Process for separating molecular species

FIELD OF THE INVENTION
The instant invention relates to a novel class of three-dimensional microporous crystalline molecular sieves, to the method of their preparation and to their use as adsorbents and catalysts. The invention relates to novel molecular sieves having at least one element capable of forming a framework oxide units, e.g., "ELO.sub.2 ", with tetrahedral oxide units of aluminum (AlO.sub.2.sup.-), phosphorus (PO.sub.2.sup.+) and silicon (SiO.sub.2). These compositions may be prepared hydrothermally from gels containing reactive compounds of silicon, aluminum and phosphorus and at least one additional element capable of forming a framework oxide unit, and preferably at least one organic templating agent which may function in part to determine the course of the crystallization mechanism and the structure of the crystalline product.
BACKGROUND OF THE INVENTION
Molecular sieves of the crystalline aluminosilicate zeolite type are well known in the art and now comprise over 150 species of both naturally occurring and synthetic compositions. In general the crystalline zeolites are formed from corner-sharing AlO.sub.2 and SiO.sub.2 tetrahedra and are characterized by having pore openings of uniform dimensions, having a significant ion-exchange capacity and being capable of reversibly desorbing an adsorbed phase which is dispersed throughout the internal voids of the crystal without displacing any atoms which make up the permanent crystal structure.
Other crystalline microporous compositions which are not zeolitic, i.e. do not contain AlO.sub.2 tetrahedra as essential framework constituents, but which exhibit the ion-exchange and/or adsorption characteristics of the zeolites are also known. Metal organosilicates which are said to possess ion-exchange properties, have uniform pores and are capable of reversibly adsorbing molecules having molecular diameters of about 6 .ANG. or less, are reported in U.S. Pat. No. 3,941,871 issued Mar. 2, 1976 to Dwyer et al. A pure silica polymorph, silicalite, having molecular sieving properties and a neutral framework containing neither cations nor cation sites is disclosed in U.S. Pat. No. 4,061,724 issued Dec. 6, 1977 to R. W. Grose et al.
A recently reported class of microporous compositions and the first framework oxide molecular sieves synthesized without silica, are the crystalline aluminophosphate compositions disclosed in U.S. Pat. No. 4,310,440 issued Jan. 12, 1982 to Wilson et al. These materials are formed from AlO.sub.2 and PO.sub.2 tetrahedra and have electrovalently neutral framework as in the case of silica polymorphs. Unlike the silica molecular sieve, silicalite, which is hydrophobic due to the absence of extra-structural cations, the aluminophosphate molecular sieves are moderately hydrophilic, apparently due to the difference in electronegativity between aluminum and phosphorus. Their intracrystalline pore volumes and pore diameters are comparable to those known for zeolites and silica molecular sieves.
In copending and commonly assigned application Ser. No. 400,438, filed July 26, 1982 (now U.S. Pat. No. 4,440,871), there is described a novel class of silicon-substituted aluminophosphates which are both microporous and crystalline. The materials have a three dimensions crystal framework of PO.sub.2.sup.+, AlO.sub.2.sup.- and SiO.sub.2 tetrahedral unites and, exclusive of any alkali metal or calcium which may optionally be present, an as-synthesized empirical chemical composition on an anhydrous basis of:
mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Si.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 0.3; the maximum value in each case depending upon the molecular dimensions of the templating agent and the available void volume of the pore system of the particular silicoaluminophosphate species involved; and "x", "y", and "z" represent the mole fractions of silicon, aluminum and phosphorus, respectively, present as tetrahedral oxides. The minimum value for each of "x", "y", and "z" is 0.01 and preferably 0.02. The maximum value for "x" is 0.98; for "y" is 0.60; and for "z" is 0.52. These silicoaluminophosphates exhibit several physical and chemical properties which are characteristic of aluminosilicate zeolites and aluminophosphates.
In copending and commonly assigned application Ser. No. 480,738, filed Mar. 31, 1983 (now U.S. Pat. No. 4,500,651) there is described a novel class of titanium-containing molecular sieves whose chemical composition in the as-synthesized and anhydrous form is represented by the unit empirical formula:
mR:(Ti.sub.x Al.sub.y P.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Ti.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of between zero and about 5.0; and "x", "y" and "z" represent the mole fractions of titanium, aluminum and phosphorus, respectively, present as tetrahedral oxides.
In copending and commonly assigned application Ser. No. 514,334, filed July 15, 1983 (now U.S. Pat. No. 4,567,029), there is described a novel class of crystalline metal aluminophosphates having three-dimensional microporous framework structures of MO.sub.2, AlO.sub.2 and PO.sub.2 tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (M.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 0.3; "M" represents at least one metal of the group magnesium, manganese, zinc and cobalt; "x", "y" and "z" represent the mole fraction of the metal "M", aluminum and phosphorus, respectively, present as tetrahedral oxides.
In copending and commonly assigned application Ser. No. 514,335, filed July 15, 1983 (now U.S. Pat. No. 4,683,217), there is described a novel class of crystalline ferroaluminophosphates having a three-dimensional microporous framework structure of FeO.sub.2, AlO.sub.2 and PO.sub.2 tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula
mR:(Fe.sub.x Al.sub.y P.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Fe.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 0.3; and "x", "y" and "z" represent the mole fraction of the iron, aluminum and phosphorus, respectively, present as tetrahedral oxides. The instant molecular sieve compositions are characterized in several ways as distinct from heretofore known molecular sieves, including the aforementioned ternary compositions. The instant molecular sieves are characterized by the enhanced thermal stability of certain species and by the existence of species heretofore unknown for binary and ternary molecular sieves.
The instant invention relates to new molecular sieve compositions having at least one element other than silicon, aluminum and phosphorus where such element is capable of forming a framework oxide unit with AlO.sub.2.sup.-, PO.sub.2.sup.+, and SiO.sub.2 tetrahedral oxide units.

DESCRIPTION OF THE FIGURES
FIG. 1 is a ternary diagram wherein parameters relating to the instant compositions are set forth as mole fractions.
FIG. 2 is a ternary diagram wherein parameters relating to preferred compositions are set forth as mole fractions.
FIG. 3 is a ternary diagram wherein parameters relating to the reaction mixtures employed in the preparation of the compositions of this invention are set forth as mole fractions.

SUMMARY OF THE INVENTION
The instant invention relates to a new class of molecular sieves in which at least one element capable of forming a framework oxide unit is provided to form crystal framework structures of SiO.sub.2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and ELO.sub.2.sup.n units wherein "EL" represents at least one element present as a framework oxide unit "ELO.sub.2.sup.n " with charge "n" where "n" may be -3, -2, -1, 0 or +1. These new molecular sieves exhibit ion-exchange, adsorption and catalytic properties and, accordingly, find wide use as adsorbents and catalysts.
The member of this novel class of compositions have crystal framework structures of SiO.sub.2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and ELO.sub.2.sup.n framework oxide units, where "n" is -3, -2, -1, 0 or +1, and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value from zero to about 0.3; "EL" represents at least one element capable of forming a framework oxide unit as hereinafter described; and "w", "x", "y" and "z" represent the mole fractions of "EL", aluminum, phosphorus and silicon, respectively, present as framework oxide units. "EL" denominates the elements present in addition to aluminum, phosphorus and silicon and may be a single element or may be two or more elements such that the molecular sieves contain one or more framework oxide units "ELO.sub.2.sup.n " in addition to framework tetrahedral oxide units SiO.sub.2, AlO.sub.2.sup.- and PO.sub.2.sup.+.
The molecular sieves of the instant invention will be generally referred to by the acronym "ELAPSO" to designate element(s) "EL" in an oxide framework of SiO.sub.2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and ELO.sub.2.sup.n oxide units. Actual class members will be identified by replacing the "EL" of the acryonym with the element(s) present as a ELO.sub.2.sup.n oxide unit(s). For example "CoAPSO" designates a molecular sieve comprised of SiO.sub.2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and CoO.sub.2.sup.-2 (and/or CoO.sub.2.sup.-1) framework oxide units, and "CoZnAPSO" designates a molecular sieve having SiO.sub.2, AlO.sub.2.sup.-, PO.sub.2.sup.+, CoO.sub.2.sup.-2 (and/or CoO.sub.2.sup.-1) and ZnO.sub.2.sup.-2 framework oxide units. To identify various structural species which make up each of the subgeneric classes, each species is assigned a number and is identified as "ELAPSO-i" wherein "i" is an integer. This designation is an arbitrary one and is not intended to denote structural relationship to another material(s) which may also be characterized by a numbering system.
DETAILED DESCRIPTION OF THE INVENTION
The instant invention relates to a new class of three-dimensional microporous crystalline molecular sieves in which at least one element capable of forming a framework oxide unit is provided to form crystal framework structures of SiO.sub.2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and ELO.sub.2.sup.n framework oxide units wherein "EL" represents at least one element capable of forming a framework oxide unit "ELO.sub.2.sup.n " with charge "n" where "n" is -3, -2, -1, 0 or +1. These new molecular sieves exhibit ion-exchange, adsorption and catalytic properties and accordingly find wide use as adsorbents and catalysts.
The ELAPSO compositions are formed with elements capable of forming framework oxide units in the presence of SiO.sub.2, AlO.sub.2.sup.- and PO.sub.2.sup.+ tetrahedral oxide units where element "EL" is at least one element capable of forming a three dimensional oxide framework in the presence of aluminum, phosphorus and silicon oxide units, and has a mean "T-O" distance in tetrahedral oxide structures of between about 1.51 Angstroms and about 2.06 Angstroms, has a cation electronegativity between about 125 kcal/g-atom and about 310 kcal/g-atom and is capable of forming stable M-O-P, M-O-Al or M-O-M bonds in crystalline three dimensional oxide structures where the "M-O" bond dissociation energy, D.degree., is greater than about 59 kcal/mole at 298.degree. K. The use of "M" in the aforementioned discussion on bond energies is one of convenience since the prior art has heretofore employed "M" to designate the element (EL) bonded to oxygen. For the purposes of discussion herein any reference to M-O-P, M-O-Al, M-O-M or M-O refers to the substitution of element(s) "EL" for the "M" designation. The "T-O" distance denominates the bond length of the "T-O" bond where "T" is element(s) "EL" occupying the tetrahedral cation site and is related to the Shannon/Prewitt crystal or ionic radii. Elements known to occur in tetrahedral coordination with oxygen are discussed in: Joseph V. Smith, "Feldspar Minerals", Springer-Verlag, Berlin, New York, Vol. I, pp. 55-65 and 106-113 (1974); R. D. Shannon, Acta. Cryst., A32, p. 751 (1976); R. D. Shannon, C. T. Prewitt, Acta. Cryst., B25, p. 925 (1969); and F. Donald Bloss, "Crystallography and Crystal Chemistry", Holt, Rinehart and Winston, Inc., New York, pp. 278-279 (1971). The "T-O" distance is calculated according to the procedures heretofore employed and as discussed in, R. D. Shannon, Acta Cryst., A32, p. 751 (1976) and R. D. Shannon, C. T. Prewitt, Acta Cryst., B25, p. 925 (1969), based, repspectively, on the ionic and crystal radius of oxide ion, O.sup.2-, of 1.40 Angstroms and 1.26 Angstroms. The cation electronegtivity of element(s) "EL" is determined consistent with the procedure set forth in A. S. Povarennykh, "Crystal Chemical Classification of Minerals", Vol. I, translation from Russian by J. E. S. Bradley, Plenum Press, New York-London, p. 32 (1972). The bond dissociation energy of "M-O" is determined according to the procedures discussed in: V. I. Vedeneyev, L. V. Gurvich, V. N. Kondrat'Yev, V. A. Medvedev and Ye. L. Frankevich, "Bond Energies, Ionization Potentials and Electron Affinities," New York, St. Martins Press, English Translation, p. 29ff (1966); "The Oxide Handbook", 2nd Ed., G. V. Samsonov, ED., translation from Russian by R. K. Johnston, IFI/Plenum Data Company, pp. 86-90 (1982); and "Bond Dissociation Energies in Simple Molecules", B deB. Darwent, NSRSS-NBS 31, U.S. Dept. of Commerce, National Bureau of Standards, pp. 9-47 (1970).
Further embodiments of the instant invention relate to the molecular sieves as above defined being characterized by element(s) "EL" characterized by at least one of the following criteria:
(1) "EL" is characterized by an electronic orbital configuration selected from the group consisting of d.sup.0, d.sup.1, d.sup.2, d.sup.5, d.sup.6, d.sup.7, or d.sup.10 where the small crystal field stabilization energy of the metal ligand "-OM" favors tetrahedral coordination of element EL ("EL" denominated here also as "M") with O.sup.2-, as discussed in "Inorganic Chemistry" J. E. Huheey, Harper Row, p. 348 (1978):
(2) "EL" is characterized as capable of forming stable oxo or hydroxo species in aqueous solution as evidenced by a first hydrolysis constant, K.sub.11, greater than 10.sup.-14, as discussed in "The Hydrolysis of Cations", C. F. Baes and R. E. Mesmer, John Wiley & Sons (1976);
(3) "EL" is selected from the group of elements known to occur in crystal structure types geometrically related to the different silica modifications, quartz, cristobalite or tridymite, as discussed in E. Parthe, "Crystal Chemistry of Tetrahedral Structures", Gordon and Breach, New York, London, pp. 66-68 (1964); and
(4) "EL" is an element which in its cation form is classified by Pearson, (J. E. Huheey, "Inorganic Chemistry", Harper & Row, p. 276 (1978)) as "hard" or "borderline" acids which interact with the "hard" base O.sup.2- to form more stable bonds than the cations classified as "soft" acids.
In one embodiment of the invention element "EL" is preferably at least one element selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc.
The relative amounts of silicon, aluminum, phosphorus and element(s) "EL" are expressed by the empirical chemical formula (anhydrous):
mR:(EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
where "w", "x", "y" and "z" represent the mole fractions of said element(s) "EL", aluminum, phosphorus, and silicon, respectively. When "EL" comprises two or more elements, "w" represents the mole fractions of said elements (EL.sub.1, EL.sub.2, EL.sub.3, EL.sub.4, etc.) and "w" equals the sum of "w.sub.1 ", "w.sub.2 ", "w.sub.3 ", "w.sub.4 ", etc., wherein "w.sub.1 ", "w.sub.2 ", "w.sub.3 ", "w.sub.4 " and etc. represent the individual mole fractions of elements EL.sub.1, EL.sub.2, EL.sub.3, EL.sub.4 and etc. and each has a value of at least 0.01.
The molecular sieves of the instant invention have three-dimensional microporous crystalline framework structures of ELO.sub.2.sup.n, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 framework oxide units having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
wherein "R" represents an organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; "EL" represents at least one element capable of forming a three dimensional oxide framework has a mean "T-O" distance in tetrahedral oxide structures of between about 1.51 Angstroms and about 2.06 Angstroms, has a cation electronegativity between about 125 kcal/g-atom to 310 kcal/g-atom and is capable of forming stable M-O-P, M-O-Al or M-O-M bonds in crystalline three dimensional oxide structures where the "M-O" bond dissociation energy, D.degree., is greater than about 59 kcal/mole at 298.degree. K; and "w", "x", "y" and "z" represent the mole fractions of element(s) "EL", aluminum, phosphorus and silicon, respectively, present as framework oxide units. The use of "M" in the aforementioned discussion on bond energies is one of convenience since the prior art has heretofore employed "M" to dominate the element (EL) bonded to oxygen. For the purpose of discussion herein any reference to M-O-P, M-O-Al, M-O-M or M-O refers to the substitution of element(s) "EL" for the "M" designation. The mole fractions "w", "x", "y" and "z" are generally defined as being within the pentagonal compositional area defined by points A, B, C, D and E of the ternary diagram of FIG. 1, said points A, B, C, D and E of FIG. 1 having the following values for "w", "x", "y", and "z":
______________________________________ Mole FractionPoint x y (z + w)______________________________________A 0.60 0.39-(0.01)p 0.01(p + 1)B 0.39-(0.01p) 0.60 0.01(p + 1)C 0.01 0.60 0.39D 0.01 0.01 0.98E 0.60 0.01 0.39______________________________________
where "p" is an integer corresponding to the number of elements "EL" in the (EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 constituent and is preferably an integer from one (1) to fourteen (14).
In a preferred subclass of the ELAPSO molecular sieves the values of "w", "x", "y" and "z", where "w" is as above defined, in the above formula are within the tetragonal compositional area defined by points a, b, c and d of the ternary diagram which is FIG. 2, said points a, b, c and d representing the following values for "w", "x", "y" and "z";
______________________________________ Mole FractionPoint x y (z + w)______________________________________a 0.60 0.39-0.01p 0.01(p + 1)b 0.39-(0.01p) 0.60 0.01(p + 1)c 0.10 0.55 0.35d 0.55 0.10 0.35______________________________________
where "p" is as above defined.
While it is believed that the elements "EL", aluminum, phosphorus and silicon in the framework constituents are present in tetrahedral coordination with oxygen, i.e. as tetrahedral oxide units, it is theoretically possible that some fraction of these framework constituents are present in coordination with five or six oxygen atoms. The convenient reference herein to the framework oxide units are represented by formulae which indicate tetrahedral oxide units, although as above noted other than tetrahedral coordination may exist. It is not, moreover, necessarily the case that all the elements "EL" of any given synthesized product be part of the framework in the aforementioned types of coordination with oxygen. Some of each constituent may be in some as yet undetermined form.
The ELAPSOs of this invention are useful as adsorbents, catalysts, ion-exchangers, and the like in much the same fashion as aluminosilicates have been employed heretofore, although their chemical and physical properties are not necessarily similar to those observed for aluminosilicates.
ELAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing active sources of element(s) "EL", silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent which is preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at an effective temperature which is preferably between about 50.degree. C. and about 250.degree. C., more preferably between 100.degree. C. and 200.degree. C., until crystals of the ELAPSO product are obtained, usually an effective crystallization time of from several hours to several weeks. Generally, effective crystallization times of from about 2 hours to about 30 days are employed with typically from 4 hours to about 20 days being employed to obtain ELAPSO products. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the ELAPSO compositions of the instant invention, it is preferred to employ a reaction mixture composition expressed in terms of molar ratios as follows:
aR:(EL.sub.r Al.sub.s P.sub.t Si.sub.u)O.sub.2 :bH.sub.2 O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300; "EL" represents at least one element, as herein before described, capable of forming a framework oxide unit, ELO.sub.2.sup.n, with SiO.sub.2, AlO.sub.2.sup.- and PO.sub.2.sup.+ tetrahedral oxide units; "n" has a value of -3, -2, -1, 0 or +1; and "r", "s", "t", "u" represent the mole fractions of element "EL", aluminum, phosphorus, and silicon respectively, and each has a value of at least 0.01. In a preferred embodiment the reaction mixture is selected such that the mole fractions " r", "s", "t", and "u" are generally defined as being within the pentagonal compositional area defined by points E, F, G, H, and I of the ternary diagram of FIG. 3. Points E, F, G, H, and I of FIG. 3 have the following values for "r", "s", "t", and "u":
______________________________________Mole FractionPoint s t (u + r)______________________________________F 0.60 0.38 0.02G 0.38 0.60 0.02H 0 01 0.60 0.39I 0.01 0.01 0.98J 0.60 0.01 0.39______________________________________
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "r", "s", "t", and "u" such that (r+s+t+u)=1.00 mole, whereas in the examples the reaction mixtures may be expressed in terms of molar oxide ratios normalized to the moles of P.sub.2 O.sub.5. This latter form is readily converted to the former form by routine calculations by dividing the number of moles of each component (including the template and water) by the total number of moles of elements "EL", aluminum, phosphorus and silicon which results in normalized mole fractions based on total moles of the aforementioned components.
In forming reaction mixtures from which the ELAPSO molecular sieves are formed an organic templating agent is preferably employed and may be any of those heretofore proposed for use in the synthesis of conventional zeolite aluminosilicates. In general these compounds contain elements of Group VA of the Periodic Table of Elements, particularly nitrogen, phosphorus, arsenic and antimony, preferably nitrogen or phosphorous and most preferably nitrogen, which compounds also contain at least one alkyl or aryl group having from 1 to 8 carbon atoms. Particularly preferred compounds for use as templating agents are the amines, quarternary phosphonium and quaternary ammonium compounds, the latter two being represented generally by the formula R.sub.4 X.sup.+ wherein "X" is nitrogen or phosphorous and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms. Polymeric quaternary ammonium salts such as [(C.sub.14 H.sub.32 N.sub.2)(OH.sub.2 ].sub.x wherein "x" has a value of at least 2 are also suitably employed. The mono-, di- and tri-amines are advantageously utilized, either alone or in combination with a quaternary ammonium compound or other templating compound. Mixtures of two or more templating agents may either produce mixtures of the desired ELAPSOs or the more strongly directing templating species may control the course of the reaction with the other templating species serving primarily to establish the pH conditions of the reaction gel. Representative templating agents include: tetramethylammonium; tetraethylammonium; tetrapropylammonium; tetrabutylammonium ions; tetrapentylammonium ions; di-n-propylamine; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylamine; N,N-dimethylethanolamine; choline; N,N'-dimethylpiperazine; 1,4-diazabicyclo(2,2,2)octane; N-methyldiethanolamine, N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo(2,2,2)octane ion; di-n-butylamine, neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; and 2-imidazolidone. Not every templating agent will direct the formation of every species of ELAPSO, i.e., a single templating agent may, with proper manipulation of the reaction conditions, direct the formation of several ELAPSO compositions, and a given ELAPSO composition can be produced using several different templating agents.
The source of silicon may be silica, either as a silica sol or as fumed silica, a reactive solid amorphous precipitated silica, silica gel, alkoxides of silicon, silica containing clays silicic acid or alkali metal silicate and mixtures thereof.
The most suitable phosphorus source yet found for the present process is phosphoric acid, but organic phosphates such as triethyl phosphate have been found satisfactory, and so also have crystalline or amorphous aluminophosphates such as the AlPO.sub.4 compositions of U.S. Pat. No. 4,310,440. Organo-phosphorus compounds, such as tetrabutylphosphonium bromide do not, apparently, serve as reactive sources of phosphorus, but these compounds do function as templating agents. Conventional phosphorus salts such as sodium metaphosphate, may be used, at least in part, as the phosphorus source, but are not preferred.
The preferred aluminum source is either an aluminum alkoxide, such as aluminum isoproproxide, or pseudoboehmite. The crystalline or amorphous aluminophosphates which are a suitable source of phosphorus are, of course, also suitable sources of aluminum. Other sources of aluminum used in zeolite synthesis, such as gibbsite, aluminum-containing clays, sodium aluminate and aluminum trichloride, can be employed but are not preferred.
The element(s) "EL" can be introduced into the reaction system in any form which permits the formation in situ a of reactive form of the element, i.e., reactive to form a framework oxide unit of element "EL". Compounds of element(s) "EL" which may be employed include oxides, hydroxides, alkoxides, nitrates, sulfates, halides, carboxylates and mixtures thereof. Representative compounds which may be employed include: carboxylates of arsenic and beryllium; cobalt chloride hexahydrate, alpha cobaltous iodide; cobaltous sulfate; cobalt acetate; cobaltous bromide; cobaltous chloride; boron alkoxides; chromium acetate; gallium alkoxides; zinc acetate; zinc bromide; zinc formate; zinc iodide; zinc sulfate heptahydrate; germanium dioxide; iron (II) acetate; lithium acetate; magnesium acetate; magnesium bromide; magnesium chloride; magnesium iodide; magnesium nitrate; magnesium sulfate; manganese acetate; manganese bromide; manganese sulfate; titanium tetrachloride; titanium carboxylates; titanium acetate; zinc acetate; and the like.
While not essential to the synthesis of ELAPSO compositions, stirring or other moderate agitation of the reaction mixture and/or seeding the reaction mixture with seed crystals of either the ELAPSO species to be produced or a topologically similar aluminophosphate, aluminosilicate or molecular sieve composition, facilitates the crystallization procedure.
After crystallization the ELAPSO product may be isolated and advantageously washed with water and dried in air. The as-synthesized ELAPSO generally contains within its internal pore system at least one form of any templating agent employed in its formation. Most commonly this organic moiety, derived from any organic template, is present, at least in part, as a charge-balancing cation as is generally the case with as-synthesized aluminosilicate zeolites prepared from organic-containing reaction systems. It is possible, however, that some or all of the organic moiety may be an occluded molecular species in a particular ELAPSO species. As a general rule the templating agent, and hence the occluded organic species, is too large to move freely through the pore system of the ELAPSO product and must be removed by calcining the ELAPSO at temperatures of 200.degree. C. to 700.degree. C. to thermally degrade the organic species. In some instances the pores of the ELAPSO compositions are sufficiently large to permit transport of the templating agent, particularly if the latter is a small molecule, and accordingly complete or partial removal thereof may be accomplished by conventional desorption procedures such as carried out in the case of zeolites. It will be understood that the term "as-synthesized" as used herein does not include the condition of ELAPSO species wherein any organic moiety occupying the intracrystalline pore system as a result of the hydrothermal crystallization process has been reduced by post-synthesis treatment such that the value of "m" in the composition formula:
mR:(M.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
has a value of less than 0.02. The other symbols of the formula are as defined hereinabove. In those preparations in which an alkoxide is employed as the source of element(s) "EL", aluminum, phosphorous and/or silicon, the corresponding alcohol is necessarily present in the reaction mixture since it is a hydrolysis product of the alkoxide. It has not been determined whether this alcohol participates in the syntheses process as a templating agent. For the purposes of this application, however, this alcohol is arbitrarily omitted from the class of templating agents, even if it is present in the as-synthesized ELAPSO material.
Since the present ELAPO compositions are formed from AlO.sub.2.sup.-, PO.sub.2.sup.+, SiO.sub.2 and ELO.sub.2.sup.n framework oxide units which, respectively, have a net charge of -1, +1, 0 and "n", where "n" is -3, -2, -1, 0 or +1, the matter of cation exchangeability is considerably more complicated than in the case of zeolitic molecular sieves in which, ideally, there is a stoichiometric relationship between AlO.sub.2.sup.- tetrahedra and charge-balancing cations. In the instant compositions, an AlO.sub.2.sup.- tetrahedron can be balanced electrically either by association with a PO.sub.2.sup.+ tetrahedron or a simple cation such as an alkali metal cation, a cation of the element "EL" present in the reaction mixture, or an organic cation derived from the templating agent. Similarly, an ELO.sub.2.sup.n oxide unit can be balanced electrically by association with PO.sub.2.sup.+ tetrahedra, a simple cation such as an alkali metal cation, a cation of the metal "EL", organic cations derived from the templating agent, or other divalent or polyvalent metal cations introduced from an extraneous source. It has also been postulated that non-adjacent AlO.sub.2.sup.- and PO.sub.2.sup.+ tetrahedral pairs can be balanced by Na.sup.+ and OH.sup.- respectively [Flanigen and Grose, Molecular Sieve Zeolites-I, ACS, Washington, D.C. (1971)].
The ELAPSO compositions of the present invention may exhibit cation-exchange capacity when analyzed using ion-exchange techniques heretofore employed with zeolitic aluminosilicates and have pore diameters which are inherent in the lattice structure of each species and which are at least about 3 .ANG. in diameter. Ion exchange of ELAPSO compositions will ordinarily be possible only after the organic moiety present as a result of synthesis has been removed from the pore system. Dehydration to remove water present in the as-synthesized ELAPSO compositions can usually be accomplished, to some degree at least, in the usual manner without removal of the organic moiety, but the absence of the organic species greatly facilitates adsorption and desorption procedures. The ELAPSO materials will have various degrees of hydrothermal and thermal stability, some being quite remarkable in this regard, and will function as molecular sieve adsorbents and hydrocarbon conversion catalysts or catalyst bases.
In the examples a stainless steel reaction vessel is utilized which is lined with an inert plastic material, polytetrafluoroethylene, to avoid contamination of the reaction mixture. In general, the final reaction mixture from which each ELAPSO composition is crystallized is prepared by forming mixtures of less than all of the reagents and thereafter incorporating into these mixtures additional reagents either singly or in the form of other intermediate mixtures of two or more reagents. In some instances the admixed reagents retain their identity in the intermediate mixture and in other cases some or all of the reagents are involved in chemical reactions to produce new reagents. The term "mixture" is applied in both cases. Further, unless otherwise specified, each intermediate mixture as well as the final reaction mixture was stirred until substantially homogeneous.
X-ray patterns of reaction products are obtained by X-ray analysis using standard X-ray powder diffraction techniques. The radiation source is a high-intensity, copper target, X-ray tube operated at 50 Kv and 40 ma. The diffraction pattern from the copper K-alpha radiation and graphite monochromator is suitably recorded by an X-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder. Flat compressed powder samples are scanned at 2.degree. (2 theta) per minute, using a two second time constant. Interplanar spacings (d) in Angstrom units are obtained from the position of the diffraction peaks expressed as 2.theta. where .theta. is the Bragg angle as observed on the strip chart. Intensities are determined from the heights of diffraction peaks after subtracting background, "I.sub.o " being the intensity of the strongest line or peak, and "I" being the intensity of each of the other peaks.
Alternatively, the X-ray patterns are obtained from the copper K-alpha radiation by use of computer based techniques using Siemens D-500 X-ray powder diffractometers, Siemens Type K-805 X-ray sources, available from Siemens Corporation, Cherry Hill, New Jersey, with appropriate computer interface.
As will be understood by those skilled in the art the determination of the parameter 2 theta is subject to both human and mechanical error, which in combination, can impose an uncertainty of about .+-.0.4.degree. (denotes plus or minus 0.4) on each reported value of 2 theta. This uncertainty is, of course, also manifested in the reported values of the d-spacings, which are calculated from the 2 theta values. This imprecision is general throughout the art and is not sufficient to preclude the differentiation of the present crystalline materials from each other and from the compositions of the prior art. In some of the X-ray patterns reported, the relative intensities of the d-spacings are indicated by the notations vs, s, m, w and vw which represent very strong, strong, medium, weak, and very weak, respectively.
In certain instances the purity of a synthesized product may be assessed with reference to its X-ray powder diffraction pattern. Thus, for example, if a sample is stated to be pure, it is intended only that the X-ray pattern of the sample is free of lines attributable to crystalline impurities, not that there are no amorphous materials present.
The molecular sieves of the instant invention may be characterized by their x-ray powder diffraction patterns and such may have one of the x-ray patterns set forth in the following Tables A through W, wherein said x-ray patterns are for both the as-synthesized and calcined forms unless otherwise noted:
TABLE A______________________________________(ELAPSO-5)2.theta. d(.ANG.) Relative Intensity______________________________________7.2-7.7 12.28-11.48 m-vs19.4-19.9 4.58-4.46 w-m20.85-21.3 4.26-4.17 w-vs22.1-22.6 4.02-3.93 m-vs25.6-26.1 3.480-3.414 vw-m______________________________________
TABLE B______________________________________(ELAPSO-11)2.theta. d(.ANG.) Relative Intensity______________________________________7.8-8.2 11.19-10.85 m-s9.0-9.8 9.83-9.03 vw-vs12.8-13.6 6.92-6.51 vw-m19.9-20.5 4.46-4.33 m-s20.8-21.8 4.27-4.08 m-vs22.0-22.6 4.04-3.93 m-vs22.6-23.1 3.93-3.85 vw-vs23.1-23.5 3.85-3.79 w-vs______________________________________
TABLE C______________________________________(ELAPSO-14)2.theta. d(.ANG.) Relative Intensity______________________________________8.6-8.9 10.3-9.93 vs13.0 6.81 w21.9-22.2 4.06-4.00 w25.4 3.51 w27.5 3.24 w29.7 3.01 w______________________________________
TABLE D______________________________________(ELAPSO-16)2.theta. d(.ANG.) Relative Intensity______________________________________11.3-11.6 7.83-7.63 w-vs18.55-18.9 4.78-4.70 vm-m21.85-22.2 4.07-4.00 m-vs22.8-23.3 3.900-3.818 w-m26.4-27.3 3.370-3.267 w-m29.6-29.9 3.018-2.988 w-m______________________________________
TABLE E______________________________________(ELAPSO-17)2.theta. d(.ANG.) Relative Intensity______________________________________7.70-7.75 11.5-11.4 vs13.4 6.61 s-vs 15.5-15.55 5.72-5.70 s19.65-19.7 4.52-4.51 w-s20.5-20.6 4.33-4.31 vs 31.8-32.00 2.812-2.797 w-s______________________________________
TABLE F______________________________________(ELAPSO-18)2.theta. d(.ANG.) Relative Intensity______________________________________ 9.6-9.65 9.21-9.16 vs 15.5-15.55 5.72-5.70 m16.9-17.1 5.25-5.19 m20.15-20.25 4.41-4.39 m20.95-21.05 4.24-4.22 m31.8-32.5 2.814-2.755 m______________________________________
TABLE G______________________________________(ELAPSO-20)2.theta. d(.ANG.) Relative Intensity______________________________________13.8-14.2 6.42-6.23 m-vs 19.6-20.15 6.53-4.41 m24.1-24.7 3.695-3.603 m-vs27.9-28.6 3.198-3.121 w 31.3-32.05 2.861-2.791 w34.35-35.0 2.610-2.601 w-m______________________________________
TABLE H______________________________________(ELAPSO-31)2.theta. d(.ANG.) Relative Intensity______________________________________8.4-9.5 10.53-9.31 w-s20.2-20.4 4.40-4.35 m22.0-22.1 4.040-4.022 m22.5-22.7 3.952-3.92 vs31.6-31.8 2.831-2.814 w-m______________________________________
TABLE J*______________________________________(ELAPSO-33)2.theta. d(.ANG.) Relative Intensity______________________________________9.25-9.55 9.56-9.26 w-m12.5-12.9 7.08-6.86 vs16.9-17.3 5.25-5.13 w-m20.45-20.9 4.34-4.25 w-m23.85-24.25 3.73-3.67 w-m26.05-26.35 3.42-3.38 w-m27.3-27.6 3.27-3.23 vs______________________________________ *as-synthesized form
TABLE K*______________________________________(ELAPSO-33)2.theta. d(.ANG.) Relative Intensity______________________________________13.15-13.4 6.73-6.61 vs18.05-18.35 4.91-4.83 m18.4-18.6 4.82-4.77 m26.55-26.7 3.36-3.34 m32.0-32.1 2.80-2.79 m______________________________________ *calcined form
TABLE L______________________________________(ELAPSO-34)2.theta. d(.ANG.) Relative Intensity______________________________________9.3-9.8 9.51-9.03 m-vs12.6-13.2 7.03-6.71 w-m15.8-16.3 5.61-5.44 vw-m20.25-21.2 4.39-4.19 w-vs24.8-25.4 3.59-3.507 vw-m30.0-30.9 2.979-2.894 vw-m______________________________________
TABLE M______________________________________(ELAPSO-35)2.theta. d(.ANG.) Relative Intensity______________________________________10.6-11.1 8.35-7.97 vw-vs13.1-13.7 6.76-6.46 vw-vs17.0-17.6 5.22-5.04 w-s 20.6-21.25 4.31-4.18 vw-m21.6-22.3 4.11-3.99 m-vs28.1-28.8 3.175-3.100 vw-m______________________________________
TABLE N______________________________________(ELAPSO-36)2.theta. d(.ANG.) Relative Intensity______________________________________7.45-8.0 11.14-11.05 vs8.1-8.3 10.91-10.65 w-m16.3-16.6 5.44-5.34 w-m18.9-19.4 4.70-4.57 w-m20.7-21.0 4.29-4.23 w-m______________________________________
TABLE O______________________________________(ELAPSO-37)2.theta. d(.ANG.) Relative Intensity______________________________________6.1-6.3 14.49-14.03 vs15.5-15.7 5.72-5.64 w-m18.5-18.8 4.80-4.72 w-m23.5-23.7 3.79-3.75 w-m26.9-27.1 3.31-3.29 w-m______________________________________
TABLE P______________________________________(ELAPSO-39)2.theta. d(.ANG.) Relative Intensity______________________________________9.2-9.6 9.61-9.21 m13.1-13.5 6.76-6.56 m17.8-18.4 4.98-4.82 w-m20.8-21.3 4.27-4.17 m-vs 22.2-22.85 4.00-3.892 m-vs 26.4-27.05 3.376-3.296 w-m______________________________________
TABLE Q______________________________________(ELAPSO-40)2.theta. d(.ANG.) Relative Intensity______________________________________7.5-7.7 11.79-11.48 vw-m8.0-8.1 11.05-10.94 s-vs12.4-12.5 7.14-7.08 w-vs13.6-13.8 6.51-6.42 m-s14.0-14.1 6.33-6.28 w-m27.8-28.0 3.209-3.187 w-m______________________________________
TABLE R______________________________________(ELAPSO-41)2.theta. d(.ANG.) Relative Intensity______________________________________13.6-13.8 6.51-6.42 w-m20.5-20.6 4.33-4.31 w-m21.1-21.3 4.21-4.17 vs22.1-22.3 4.02-3.99 m-s22.8-23.0 3.90-3.86 m23.1-23.4 3.82-3.80 w-m25.5-25.9 3.493-3.44 w-m______________________________________
TABLE S______________________________________(ELAPSO-42)2.theta. d(.ANG.) Relative Intensity______________________________________7.15-7.4 12.36-11.95 m-vs12.5-12.7 7.08-6.97 m-s21.75-21.9 4.09-4.060 m-s 24.1-24.25 3.69-3.67 vs27.25-27.4 3.273-3.255 s30.05-30.25 2.974-2.955 m-s______________________________________
TABLE T______________________________________(ELAPSO-43)2.theta. d(.ANG.) Relative Intensity______________________________________12.3-12.95 7.20-6.83 m-vs16.8-17.45 5.28-5.09 vw-w21.45-21.85 4.145-4.071 m-vs27.1-27.85 3.291-3.232 w-vs32.4-33.2 2.763-2.699 vw-m______________________________________
TABLE U______________________________________(ELAPSO-44)2.theta. d(.ANG.) Relative Intensity______________________________________9.2-9.6 9.61-9.21 m-vs15.9-16.3 5.57-5.44 vw-m20.5-21.0 4.33-4.23 m-vs24.3-25.1 3.66-3.548 w-m30.5-31.1 2.931-2.876 vw-m______________________________________
TABLE V______________________________________(ELAPSO-46)2.theta. d(.ANG.) Relative Intensity______________________________________7.2-8.1 12.28-10.92 vs12.9-13.6 6.86-6.51 vw21.2-22.2 4.19-4.501 vw-m 22.5-23.45 3.95-3.793 vw-m26.6-27.9 3.351-3.198 vw-m______________________________________
TABLE W______________________________________(ELAPSO-47)2.theta. d(.ANG.) Relative Intensity______________________________________9.4-9.6 9.41-9.21 vs12.8-13.1 6.92-6.76 vw-m16.0-16.3 5.54-5.44 vw-m20.5-21.0 4.31-4.23 m-vs24.6-25.3 3.613-3.526 vs-m30.6-31.1 2.921-2.876 vw-m______________________________________
The following examples are provided to further illustrate the invention and are not intended to be limiting thereof:
ELAPSO MOLECULAR SIEVE COMPOSITIONS
The ELAPSO molecular sieves of the invention may be prepared having one or more elements present as framework oxide units such that the ELAPSO molecular sieves contain framework oxide units "ELO.sub.2 ", ALO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 where "EL" denominates at least one element capable of forming a framework oxide unit with AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units. The following ELAPSO molecular sieves are representative of molecular sieves prepared according to the instant invention:
COBALT-ALUMINUM-PHOSPHORUS-SILICON-OXIDE MOLECULAR SIEVES
Molecular sieves containing cobalt, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents
In the following examples the CoAPSO compositions were prepared using numerous reagents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:
(a) Alipro: aluminum isoproproxide;
(b) CATAPAL: Trademark of Condea Corporation for pseudoboehmite;
(c) LUDOX-LS: Trademark of DuPont for an aqueous solution of 30 weight percent SiO.sub.2 and 0.1 weight percent Na.sub.2 O;
(d) Co(Ac).sub.2 : cobalt acetate Co(C.sub.2 H.sub.3 O.sub.2).sub.2.4H.sub.2 O;
(e) CoSO.sub.4 : cobalt sulfate (CoSO.sub.4.7H.sub.2 O);
(f) H.sub.3 PO.sub.4 : 85 weight percent phosphoric acid in water;
(g) TBAOH: tetrabutylammonium hydroxide (25 wt % in methanol);
(h) Pr.sub.2 NH: di-n-propylamine, (C.sub.3 H.sub.7).sub.2 NH;
(i) Pr.sub.3 N: tri-n-propylamine, (C.sub.3 H.sub.7).sub.3 N;
(j) Quin: Quinuclidine (C.sub.7 H.sub.13 N);
(k) MQuin: Methyl Quinuclidine hydroxide, (C.sub.7 H.sub.13 NCH.sub.3 OH);
(l) C-hex; cyclohexylamine;
(m) TEAOH; tetraethylammonium hydroxide (40 wt. % in water);
(n) DEEA: diethanolamine;
(o) TPAOH: tetrapropylammonium hydroxide (40 wt. % in water); and
(p) TMAOH: tetramethylammonium hydroxide (40 wt. % in water)
Preparative Procedure
The CoAPSO compositions were prepared by preparing reaction mixtures having a molar composition expressed as:
eR:fCoO:hAl.sub.2 O.sub.3 :iP.sub.2 O.sub.5 :gSiO.sub.2 :jH.sub.2 O
wherein e, f, h, i, g and j represent the moles of template R, cobalt (expressed as the oxide), Al.sub.2 O.sub.3, P.sub.2 O.sub.5 (H.sub.3 PO.sub.4 expressed as P.sub.2 O.sub.5), SiO.sub.2 and H.sub.2 O, respectively. The values for e, f, h, i, g and j were as set forth in the hereinafter discussed preparative examples.
The reaction mixtures were prepared by forming a starting reaction mixture comprising the H.sub.3 PO.sub.4 and one half of the water. This mixture was stirred and the aluminum source (Alipro or CATAPAL) added. The resulting mixture was blended until a homogeneous mixture was observed. The LUDOX-LS was then added to the resulting mixture and the new mixture blended until a homogeneous mixture was observed. The cobalt source (Co(Ac).sub.2, Co(SO.sub.4) or mixtures thereof) was dissolved in the remaining water and combined with the first mixture. The combined mixture was blended until a homogenous mixture was observed. The organic templating agent was added to this mixture and blended for about two to four minutes until a homogenous mixture was observed. The resulting mixture (final reaction mixture) was placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150.degree. C., 200.degree. C. or 225.degree. C.) for a time. Alternatively, if the digestion temperature was 100.degree. C. the final reaction mixture was placed in a lined (polytetrafluoroethylene) screw top bottle for a time. All digestions were carried out at the autogeneous pressure. The products were removed from the reaction vessel cooled and evaluated as set forth hereinafter.
The following examples are provided to further illustrate the invention and are not intended to be limiting thereof:
EXAMPLES 1A TO 31A
CoAPSO molecular sieves were prepared according to the above described procedure and the CoAPSO products determined by x-ray analysis. The results of examples 1A to 31A are set forth in Tables I-A and II-A. Tables I-A and II-A also contain examples AA to EA wherein X-ray analysis of the reaction mixture product did not show CoAPSO products.
In the Tables I-A and II-A, the reaction mixtures are described as the ratio of molar oxides:
eR:fCoO:0.9Al.sub.2 O.sub.3 :0.9P.sub.2 O.sub.5 :gSiO.sub.2 :50H.sub.2 O
where "e", "R", "f" and "g" are as above defined. Examples were prepared using this reaction mixture unless otherwise noted in Tables I-A to II-A. The values for "e", "f" and "g" are given in Tables I-A and II-A.
TABLE I-A__________________________________________________________________________Example Template e f g Temp (.degree.C.) Time (days) CoAPSO Product(s).sup.1__________________________________________________________________________1A Quin 1 0.2 0.2 150 4 CoAPSO-16; CoAPSO-352A Quin 1 0.2 0.2 150 10 CoAPSO-16: CoAPSO-353A Quin 1 0.2 0.2 200 4 CoAPSO-16; CoAPSO-354A Quin 1 0.2 0.2 200 10 CoAPSO-16; CoAPSO-355A Quin 1 0.2 0.2 100 4 CoAPSO-35; CoAPSO-166A Quin 1 0.2 0.2 100 10 CoAPSO-16; CoAPSO-357A MQuin 1 0.2 0.2 150 2 CoAPSO-35; CoAPSO-178A MQuin 1 0.2 0.2 150 7 CoAPSO-35.sup.9A MQuin 1 0.2 0.2 200 2 CoAPSO-35.sup.10A MQuin 1 0.2 0.2 200 7 CoAPSO-35.sup. 11A.sup.2,3 TBAOH 2 0.4 0.4 200 4 CoAPSO-36; CoAPSO-5 12A.sup.2,3 TBAOH 2 0.4 0.4 200 10 CoAPSO-36; CoAPSO-5__________________________________________________________________________ .sup.1 Major species as identified by xray powder diffraction pattern of product, except that when two or more species were identified the species are listed in the order of their predominence in the product. .sup.2 The molar amount of Al.sub.2 O.sub.3 was 0.8 instead of 0.9. .sup.3 Send crystals of CoAPO36 were employed in this examples, as disclosed in U.S. Ser. No. 514,334, filed July 15, 1983.
TABLE II-A__________________________________________________________________________Example Template e f g Temp (.degree.C.) Time (days) CoAPSO Product(s).sup.1__________________________________________________________________________13A C-hex 1.0 0.2 0.6 150 4 CoAPSO-44; CoAPSO-5 CoAPSO-13.sup.14A C-hex 1.0 0.2 0.6 150 10 CoAPSO-44; CoAPSO-5 CoAPSO-13.sup.15A C-hex 1.0 0.2 0.6 200 4 CoAPSO-44.sup.16A C-hex 2.0 0.2 0.6 150 4 CoAPSO-44; CoAPSO-1317A C-hex 2.0 0.2 0.6 150 10 CoAPSO-44; CoAPSO-1318A C-hex 2.0 0.2 0.6 200 4 CoAPSO-44.sup.19A C-hex 2.0 0.2 0.6 200 10 CoAPSO-44.sup.20A Pr.sub.3 N 1.0 0.2 0.2 150 4 CoAPSO-5 .sup.21A Pr.sub.3 N 1.0 0.2 0.2 150 11 CoAPSO-5 .sup.22A Pr.sub.3 N 1.0 0.2 0.2 200 4 CoAPSO-5 .sup.23A Pr.sub.3 N 1.0 0.2 0.2 200 11 CoAPSO-5 .sup.24A Pr.sub.3 N 1.0 0.2 0.2 150 2 CoAPSO-5 .sup.25A Pr.sub.3 N 1.0 0.2 0.2 150 15 CoAPSO-5 .sup.26A Pr.sub.3 N 1.0 0.2 0.2 200 2 CoAPSO-5 .sup.27A Pr.sub.3 N 1.0 0.2 0.2 200 15 CoAPSO-5 .sup.28A Pr.sub.3 N 1.0 0.2 0.2 150 21 CoAPSO-529A Pr.sub.3 N 1.5 0.2 0.2 150 3 CoAPSO-5; CoAPSO-3630A Pr.sub.3 N 1.5 0.2 0.2 150 10 CoAPSO-5; CoAPSO-3631A Pr.sub.3 N 1.5 0.2 0.2 200 3 CoAPSO-5; CoAPSO-36 AA* TBAOH 2.0 0.4 0.4 150 4 -- BA* TBAOH 2.0 0.4 0.4 150 10 --CA Pr.sub.3 N 1.0 0.2 0.2 100 4 --DA Pr.sub.3 N 1.0 0.2 0.2 100 11 --EA Pr.sub.3 N 1.0 0.2 0.2 200 21 --__________________________________________________________________________ .sup.1 Major species as identified by xray powder diffraction pattern of product, except that when two or more species were identified the species are listed in the order of their predominence in the product. A "--" indicates that Xray analysis failed to show CoAPSO products. *The molar amount of Al.sub.2 O.sub.3 was 0.8 instead of 0.9.
EXAMPLES 32A TO 61A
Examples 32A to 61A were carried out using di-n-propylamine as the organic templating agent. The preparative procedure was as above described except that in examples 39A to 45A and 53A to 61A the preparative procedure was modified such that the cobalt acetate was added to the phosphoric acid and water, followed by addition of the aluminum source, silicon source and then the organic templating agent. The aluminum source in examples 32A to 45A, 60A and 61A was aluminum isoproproxide and in examples 46A to 59A the aluminum source was CATAPAL. The reaction mixtures for examples 32A to 61A are described in terms of the molar oxide ratios: ePr.sub.2 NH:0.2CoO:0.9Al.sub.2 O.sub.3 :0.9P.sub.2 O.sub.5 ;0.2SiO.sub.2 :50H.sub.2 O where "e" is the moles of template Pr.sub.2 NH and where "e" was one (1) for examples 32A to 35A, 42A to 45A, 49A to 52A, 56A to 61A and "e" was two (2) for examples 36A to 41A, 46A to 48A, 53A to 55A. Examples FA, GA, HA and IA are reaction mixtures where X-ray analysis of the reaction products did not show CoAPSO products. Examples 32 to 61 and F, G, H, and I are set forth in Table III.
TABLE III-A__________________________________________________________________________Example Temp (.degree.C.) Time (days) CoAPSO Product(s).sup.1__________________________________________________________________________32A 150 4 CoAPSO-11; CoAPSO-3933A 150 11 CoAPSO-11; CoAPSO-46; CoAPSO-3934A 200 4 CoAPSO-11; CoAPSO-39; CoAPSO-4635A 200 11 CoAPSO-11; CoAPSO-39; CoAPSO-536A 150 10 CoAPSO-4637A 200 4 CoAPSO-11; CoAPSO-5; CoAPSO-3938A 200 10 CoAPSO-11; CoAPSO-539A 150 10 CoAPSO-4640A 200 4 CoAPSO-11; CoAPSO-5; CoAPSO-39; CoAPSO-4641A 200 10 CoAPSO-11; CoAPSO-5; CoAPSO-39; CoAPSO-4642A 150 4 CoAPSO-1143A 150 11 CoAPSO-11; CoAPSO-4644A 200 4 CoAPSO-11; CoAPSO-3945A 200 11 CoAPSO-11; CoAPSO-3946A 150 4 CoAPSO-4647A 150 10 CoAPSO-46; CoAPSO-1148A 200 4 CoAPSO-46; CoAPSO-1149A 150 10 CoAPSO-1150A 150 4 CoAPSO-1151A 200 10 CoAPSO-1152A 200 4 CoAPSO-1153A 150 10 CoAPSO-11; CoAPSO-4654A 200 4 CoAPSO-46; CoAPSO-11; CoAPSO-2055A 200 10 CoAPSO-46; CoAPSO-11; CoAPSO-2056A 150 4 CoAPSO-1157A 150 10 CoAPSO-1158A 200 4 CoAPSO-1159A 200 10 CoAPSO-1160A 150 4 CoAPSO-1161A 150 4 CoAPSO-11FA 100 4 --GA 100 11 --HA 150 4 --IA 150 4 --__________________________________________________________________________ .sup.1 Major species as identified by xray powder diffraction pattern of product, except that when two or more species were identified the species are listed in the order of their predominence in the product. A "--" indicates that Xray analysis failed to show CoAPSO products.
EXAMPLES 62A to 83A
Examples 62A to 83A were carried out according to the preparative procedure employed in examples 1A to 31A except that the organic templating agent was as TEAOH (tetraethylammonium hydroxide). The reaction mixtures for examples 62A to 83A were:
1.0TEAOH:fCoO:0.9Al.sub.2 O.sub.3 :0.9P.sub.2 O.sub.5 :gSiO.sub.2 :5OH.sub.2 O
wherein "f" was 0.2 except that "f" was 0.1 for examples 78A to 79A and was 0.05 for examples 80A to 83A; and g was 0.2 for examples 62A to 70A and was 0.6 for examples 71A to 83A. The reactive cobalt source was cobalt (II) sulfate for examples 62A to 70A and cobalt (II) acetate for examples 71A to 83A.
The results of examples 62A to 83A are set forth in Table IV-A.
TABLE IV-A______________________________________Example Temp (.degree.C.) Time (days) CoAPSO Product(s).sup.1______________________________________62A 150 4 CoAPSO-34; CoAPSO-563A 150 12 CoAPSO-34; CoAPSO-564A 150 12 CoAPSO-3465A 200 4 CoAPSO-34; CoAPSO-566A 200 12 CoAPSO-5; CoAPSO-3467A 200 12 CoAPSO-3468A 100 4 CoAPSO-3469A 100 12 CoAPSO-3470A 100 12 CoAPSO-3471A 100 2 CoAPSO-3472A 100 7 CoAPSO-3473A 150 2 CoAPSO-34; CoAPSO-574A 150 13 CoAPSO-34; CoAPSO-575A 200 2 CoAPSO-5; CoAPSO-3476A 200 7 CoAPSO-5; CoAPSO-3477A 100 14 CoAPSO-3478A 100 14 CoAPSO-3479A 100 28 CoAPSO-3480A 100 10 CoAPSO-3481A 100 20 CoAPSO-3482A 100 2 CoAPSO-3483A 100 4 CoAPSO-34______________________________________ .sup.1 Major species as indentified by Xray powder diffraction pattern of product, except that when two or more species were identified the species are listed in the order of their predominance in the product.
EXAMPLES 84A TO 106A
Examples 84A to 106A were carried out according to the preparative procedure employed in examples 1A to 31A except the organic template was as is shown in Table V-A. The reaction mixture was:
eR:f5CoO:0.9Al.sub.2 O.sub.3 :0.9P.sub.2 O.sub.5 :0.6SiO.sub.2 :50H.sub.2 O
where "e" was one (1) except that "e" was 1.5 for examples 94A to 97A and "e" was 2.0 for example 104A. The results of examples 84A to 106A are set forth in Table V-A.
TABLE V-A__________________________________________________________________________Example Template e f Temp (.degree.C.) Time (days) CoAPSO Product(s).sup.1__________________________________________________________________________84A TEAOH 1.0 0.025 125 3 CoAPSO-34; CoAPSO-18;85A TEAOH 1.0 0.025 125 5 CoAPSO-34; CoAPSO-5;86A TEAOH 1.0 0.025 100 5 CoAPSO-34; CoAPSO-5;87A TEAOH 1.0 0.025 100 5 CoAPSO-34;88A TEAOH 1.0 0.025 100 3 CoAPSO-34;89A TEAOH 1.0 0.025 100 5 CoAPSO-34;90A TEAOH 1.0 0.025 100 7 CoAPSO-34;91A Quin 1.0 0.2 225 5 CoAPSO-35; CoAPSO-1692A C-hex 1.0 0.2 225 5 CoAPSO-5; CoAPSO-44.sup. 93A.sup.2 Pr.sub.3 N 1.5 0.2 150 2 CoAPSO-36;.sup. 94A.sup.2 Pr.sub.3 N 1.5 0.2 150 7 CoAPSO-36;.sup. 95A.sup.2 Pr.sub.3 N 1.5 0.2 200 2 CoAPSO-36; CoAPSO-5.sup. 96A.sup.2 Pr.sub.3 N 1.5 0.2 200 7 CoAPSO-36; CoAPSO-5.sup. 97A.sup.3 Pr.sub.2 NH 1.0 0.2 150 4 CoAPSO-31; CoAPSO-11.sup. 98A.sup.3 Pr.sub.2 NH 1.0 0.2 150 10 CoAPSO-46; CoAPSO-31.sup. 99A.sup.3 Pr.sub.2 NH 1.0 0.2 200 4 CoAPSO-31; CoAPSO-11100A.sup.3 Pr.sub.2 NH 1.0 0.2 200 10 CoAPSO-31; CoAPSO-11; CoAPSO-5; CoAPSO-46101A.sup.3 Pr.sub.2 NH 1.0 0.2 150 2 CoAPSO-31102A.sup.3 Pr.sub.2 NH 1.0 0.2 150 3 CoAPSO-31103A.sup.3 Pr.sub.2 NH 1.0 0.2 200 2 CoAPSO-31; CoAPSO-46104A DEEA 2.0 0.2 150 2 CoAPSO-47105A TMAOH 1.0 0.2 150 4 CoAPSO-20106A TMAOH 1.0 0.2 200 4 CoAPSO-20__________________________________________________________________________ .sup.1 Major species as identified by xray powder diffraction pattern of product, except that when two or more species were identified the spaces are listed in the order of their predominance in the product. .sup.2 Seed crystals of CoAPO36 were employed (copending U.S. Ser. No. 514,334, filed July 15, 1983). .sup.3 Seed crystals of AlPO.sub.4 -31 (U.S. Pat. No. 4,310,440) were employed.
EXAMPLE 107A
Samples of the products were subjected to chemical analysis. The chemical analysis for each product is given hereinafter with the example in which the CoAPSO was prepared being given in parenthesis after the designation of the CoAPSO species.
(a) The chemical analysis for CoAPSO-11 (example 35A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 31.1P.sub.2 O.sub.5 46.1CoO 6.4SiO.sub.2 3.5Carbon 5.2LOI* 11.7______________________________________ *LOI = Loss on Ingnition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.085 CoO; 0.305 Al.sub.2 O.sub.3 : 0.325 P.sub.2 O.sub.5 :0.058SiO.sub.2 ; and a formula (anhydrous basis) of:
0.07R(Co.sub.0.06 Al.sub.0.47 P.sub.0.46 Si.sub.0.04)O.sub.2
(b) The chemical analysis for CoAPSO-11 (example 42A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 32.5P.sub.2 O.sub.5 44.7CoO 4.4SiO.sub.2 1.4Carbon 3.9LOI* 15.7______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.059 CoO; 0.319 Al.sub.2 O.sub.3 : 0.315 P.sub.2 O.sub.5 : 0.023 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.05R(Co.sub.0.04 Al.sub.0.47 P.sub.0.47 Si.sub.0.02)O.sub.2
(c) The chemical analysis for CoAPSO-20 (example 106A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 27.7P.sub.2 O.sub.5 37.8CoO 4.6SiO.sub.2 10.0Carbon 9.4LOI* 18.4______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.061 CoO; 0.272 Al.sub.2 O.sub.3 : 0.266 P.sub.2 O.sub.5 : 0.166 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.20R(Co.sub.0.05 Al.sub.0.42 P.sub.0.41 Si.sub.0.13)O.sub.2
(d) The chemical analysis of CoAPSO-31 (example 101A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 32.3P.sub.2 O.sub.5 42.4CoO 4.3SiO.sub.2 3.8Carbon 2.8LOI* 16.6______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.057 CoO; 0.317 Al.sub.2 O.sub.3 : 0.299 P.sub.2 O.sub.5 : 0.063 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.04R(Co.sub.0.04 Al.sub.0.47 P.sub.0.44 Si.sub.0.05)O.sub.2
(e) The chemical analysis for CoAPSO-34 (example 69A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 28.2P.sub.2 O.sub.5 41.7CoO 4.7SiO.sub.2 1.1Carbon 5.9LOI* 23.6______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.063 CoO; 0.277 Al.sub.2 O.sub.3 : 0.294 P.sub.2 O.sub.5 : 0.018 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.06R(Co.sub.0.05 Al.sub.0.45 P.sub.0.48 Si.sub.0.02)O.sub.2
(f) The chemical analysis of CoAPSO-34 (example 72A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 28.4P.sub.2 O.sub.5 40.6CoO 4.6SiO.sub.2 2.2Carbon 7.8LOI* 23.3______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.061 CoO; 0.279 Al.sub.2 O.sub.3 : 0.282 P.sub.2 O.sub.5 : 0.037 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.08R(Co.sub.0.05 Al.sub.0.46 P.sub.0.46 Si.sub.0.03)O.sub.2
(g) The chemical analysis for CoAPSO-34 (example 79A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 31.7P.sub.2 O.sub.5 40.5CoO 2.5SiO.sub.2 3.4Carbon 8.4LOI* 20.8______________________________________ LOI* = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.033 CoO:0.311 Al.sub.2 O.sub.3 : 0.285 P.sub.2 O.sub.5 : 0.057 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.09R(Co.sub.0.03 Al.sub.0.49 P.sub.0.45 Si.sub.0.05)O.sub.2
(h) The chemical analysis of CoAPSO-34 (example 81A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 32.0P.sub.2 O.sub.5 39.6CoO 1.2SiO.sub.2 2.7Carbon 6.4LOI* 22.8______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.016 CoO; 0.314 Al.sub.2 O.sub.3 : 0.279 P.sub.2 O.sub.5 : 0.045 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.07R(Co.sub.0.01 Al.sub.0.50 P.sub.0.45 Si.sub.0.04)O.sub.2
(i) The chemical analysis of CoAPSO-34 (example 83A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 33.8P.sub.2 O.sub.5 40.6CoO 1.6SiO.sub.2 2.1Carbon 6.6LOI* 21.7______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of:
0.021 CoO:0.332Al.sub.2 O.sub.3 :0.286 P.sub.2 O.sub.5 :0.035SiO.sub.2 ;
and a formula (anhydrous basis) of:
0.07R(Co.sub.0.02 Al.sub.0.53 P.sub.0.46 Si.sub.0.03)O.sub.2
(j) The chemical analysis of CoAPSO-34 (example 77A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 30.1P.sub.2 O.sub.5 41.7CoO 4.8SiO.sub.2 2.6Carbon 9.0LOI* 19.5______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.064 CoO; 0.295 Al.sub.2 O.sub.3 : 0.294 P.sub.2 O.sub.5 : 0.043 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.09R(Co.sub.0.05 Al.sub.0.46 P.sub.0.46 Si.sub.0.03)O.sub.2
(k) The chemical analysis of CoAPSO-34 (example 89A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 31.8P.sub.2 O.sub.5 38.8CoO 0.71SiO.sub.2 2.2Carbon 6.6LOI* 24.1______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.01 CoO; 0.312 Al.sub.2 O.sub.3 : 0.273 P.sub.2 O.sub.5 : 0.037 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.07R(Co.sub.0.01 Al.sub.0.51 P.sub.0.45 Si.sub.0.03)O.sub.2
where the value for cobalt is rounded off from 0.008.
(1) The chemical analysis of CoAPSO-34 (example 90A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 32.4P.sub.2 O.sub.5 39.3CoO 0.66SiO.sub.2 3.5Carbon 7.2LOI* 23.5______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.009 CoO; 0.318 Al.sub.2 O.sub.3 : 0.277 P.sub.2 O.sub.5 : 0.058 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.08R(Co.sub.0.01 Al.sub.0.51 P.sub.0.44 Si.sub.0.05)O.sub.2
where the value for cobalt is rounded off from 0.007.
(m) The chemical analysis of CoAPSO-35 (example 10A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 27.0P.sub.2 O.sub.5 41.6CoO 4.3SiO.sub.2 4.3Carbon 13.0LOI* 22.1______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.057 CoO; 0.265 Al.sub.2 O.sub.3 : 0.290 P.sub.2 O.sub.5 : 0.054 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.14R(Co.sub.0.05 Al.sub.0.43 P.sub.0.48 Si.sub.0.04)O.sub.2
(n) The chemical analysis of CoAPSO-36 (example 93A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 29.5P.sub.2 O.sub.5 39.6CoO 5.2SiO.sub.2 6.6Carbon 3.3LOI* 18.5______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.069 CoO; 0.289 Al.sub.2 O.sub.3 : 0.279 P.sub.2 O.sub.5 : 0.110 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.03R(Co.sub.0.05 Al.sub.0.44 P.sub.0.42 Si.sub.0.08)O.sub.2
(o) The chemical analysis of CoAPSO-44 (example 19A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 26.3P.sub.2 O.sub.5 36.3CoO 4.5SiO.sub.2 10.0Carbon 13.2LOI* 22.6______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.06 CoO; 0.258 Al.sub.2 O.sub.3 : 0.256 P.sub.2 O.sub.5 : 0.166 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.18R(Co.sub.0.05 Al.sub.0.41 P.sub.0.41 Si.sub.0.13)O.sub.2
(p) The chemical analysis of CoAPSO-46 (example 36A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 31.4P.sub.2 O.sub.5 31.5CoO 6.2SiO.sub.2 2.9Carbon 4.2LOI* 27.5______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.08 CoO; 0.31 Al.sub.2 O.sub.3 : 0.22 P.sub.2 O.sub.5 : 0.05 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.06R(Co.sub.0.07 Al.sub.0.52 P.sub.0.37 Si.sub.0.04)O.sub.2
(q) The chemical analysis of CoAPSO-47 (example 104A) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 22.7P.sub.2 O.sub.5 39.8CoO 8.2SiO.sub.2 2.9Carbon 11.4LOI* 25.2______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.109 CoO; 0.223 Al.sub.2 O.sub.3 : 0.280 P.sub.2 O.sub.5 : 0.048 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.16R(Co.sub.0.09 Al.sub.0.38 P.sub.0.48 Si.sub.0.04)O.sub.2
EXAMPLE 108A
EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on clean crystals of CoAPSO products. Analysis of crystals having a morphology characteristic of the CoAPSO compositions noted hereinafter gave the following analysis based on relative peak heights:
______________________________________ Average of Spot Probes______________________________________(a) CoAPSO-11 (example 42A):Co 1.0Al 8.0P 10.0Si 1.0(b) CoAPSO-20 (example 106A):Co 0.5Al 8.0P 7.5Si 3.4(c) CoAPSO-34 (example 69A):Co 0.5Al 8.0P 10.0Si 1.0(d) CoAPSO-35 (example 10A):Co 0.5Al 9.0P 7.5Si 1.0(e) CoAPSO-36 (example 95A):Co 0.6Al 9.1P 9.4Si 2.2(f) CoAPSO-44 (example 16A):Co 1.0Al 8.0P 8.0Si 0.6(g) CoAPSO-47 (example 104A):Co 0.7Al 8.4P 9.2Si 2.8______________________________________
EXAMPLE 109A
Samples of the CoAPSO products were tested for adsorption capacities. The CoAPSO products were evaluated either in the as-synthesized form or were calcined in air or nitrogen, to remove at least part of the organic templating agent, as hereinafter set forth. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in vacuum at 350.degree. C. prior to measurement. The McBain-Bakr data for the aforementioned calcined CoAPSO products were:
______________________________________(a) CoAPSO-11 (example 61A): Kinetic Pressure Temp Wt. %Adsorbate Diameter,.ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 106 -183 6.9O.sub.2 3.46 744 -183 12.1isobutane 5.0 740 24.2 3.9cyclo-hexane 6.0 82 23.9 13.5neopentane 6.2 74l 25.3 3.6H.sub.2 O 2.65 4.6 24.9 7.1H.sub.2 O 2.65 19 24.8 21.0______________________________________ *calcined in air at 600.degree. C. for 1 hour prior to activation
The above data demonstrate that the pore size of the calcined product is about 6.0 .ANG..
______________________________________(b) CoAPSO-20 (example 106A) Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 102 -183 5O.sub.2 3.46 744 -183 6.4H.sub.2 O 2.65 4.6 23.3 10H.sub.2 O 2.65 19 23.2 14______________________________________ *calcined in air at 500.degree. C. for one hour prior to activation.
The above data demonstrate that the pore size of the calcined product is about 3.0 .ANG..
______________________________________(c) CoAPSO-31 (example 102A) Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 105 -183 6.9O.sub.2 3.46 741 -183 12.8neopentane 6.2 739 23.5 5.8H.sub.2 O 2.65 4.6 23.5 5.8H.sub.2 O 2.65 20 24.0 15.9______________________________________ *calcined in air at 500.degree. C. for 1.5 hrs prior to activation.
The above data demonstrate that the pore size of the calcined product is greater than about 6.2 .ANG..
______________________________________(d) CoAPSO-34 (example 78A) Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 103 -183 15.9O.sub.2 3.46 731 -183 28.2n-hexane 4.3 103 23.9 9.8isobutane 5.0 741 23.3 1.8H.sub.2 O 2.65 4.6 23.8 11.3H.sub.2 O 2.65 18.5 24.0 28.9______________________________________ *calcined in nitrogen at 425.degree. C. for 2 hrs prior to activation.
The above data demonstrate that the pore size of the calcined product is about 4.3 .ANG..
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________(e) CoAPSO-34 (example 89A)O.sub.2 3.46 105 -183 18.6O.sub.2 3.46 741 -183 28.8isobutane 5.0 108 23.9 9.9n-hexane 4.3 742 23.3 1.2H.sub.2 O 2.65 4.6 23.8 10.7H.sub.2 O 2.65 20.0 24.0 30.1______________________________________ *calcined in air at 600.degree. C. for one hour prior to activation.
(f) CoAPSO-35 (example 8A)______________________________________O.sub.2 3.46 103 -183 11.7O.sub.2 3.46 731 -183 15.5isobutane 5.0 741 24.5 0.6n-hexane 4.3 103 24.4 3.5H.sub.2 O 2.65 4.6 24.4 14.3H.sub.2 O 2.65 18.5 23.9 22.7______________________________________ *calcined in nitrogen at 500.degree. C. for 2.0 hours prior to activation
The above data demonstrate that the pore size of the calcined product is about 4.3 .ANG..
______________________________________(g) CoAPSO-44 (example 19A) Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 103 -183 24.8O.sub.2 3.46 731 -183 31.4n-hexane 4.3 103 24.4 7.4isobutane 5.0 741 24.5 0.3H.sub.2 O 2.65 4.6 24.4 27.8H.sub.2 O 2.65 18.5 23.9 35.1______________________________________ *calcined in air at 500.degree. C. for 1.25 hrs. prior to activation.
The above data demonstrate that the pore size of the calcined product is about 4.3 .ANG..
______________________________________(h) CoAPSO-47 (example 104A) Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 102 -183 4.1O.sub.2 3.46 744 -183 4.9isobutane 5.0 746 24.1 0.6n-hexane 4.3 95 23.6 1.3H.sub.2 O 2.65 4.6 23.3 9.6H.sub.2 O 2.65 19 23.2 14.3______________________________________ *calcined in air at 500.degree. C. for 1.5 hrs. prior to activation.
The above data demonstrate that the pore size of the calcined product is about 4.3 .ANG..
EXAMPLE 110A
(a) The as-synthesized CoAPSO-5 of example 76A was subjected to analysis by x-ray. The CoAPSO-5 product was characterized by the x-ray powder diffraction pattern of Table VII-A below:
TABLE VII-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________7.4 11.95 1009.6* 9.21 6512.9** 6.86 1914.1* 6.28 1014.9 5.95 2616.0* 5.54 3217.8* 4.98 1319.8 4.48 6120.5* 4.33 5521.1 4.21 7422.4** 3.97 9423.0* 3.87 1024.8 3.59 1625.2* 3.53 1626.0** 3.427 4227.4* 3.255 1328.2* 3.164 1029.1 3.069 1929.5* 3.028 1030.1 2.969 2930.6* 2.921 2331.1* 2.876 1933.7** 2.660 1034.5** 2.600 1937.0 2.430 737.7 2.386 1641.5 2.176 742.2 2.141 843.7 2.071 744.9** 2.019 747.8** 1.903 1048.9* 1.863 1055.8 1.647 10______________________________________ *peak resulting from CoAPSO34 **peak resulting from CoAPSO34 and CoAPSO5
(b) CoAPSO-5, of example 21A was calcined in air at 600.degree. for four hours. The calcined product was characterized by the x-ray powder diffraction pattern of Table VIII-A below:
TABLE VIII-A______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________7.4 11.95 10012.9 6.86 2214.8 5.99 1319.7 4.51 3920.3* 4.37 8321.0 4.23 7421.4* 4.15 9922.4 3.97 7422.9* 3.88 3524.4 3.65 1325.9 3.440 3027.1** 3.290 1728.1* 3.175 2629.0 3.079 2630.1 2.969 3033.7 2.660 1334.6 2.592 2235.6* 2.522 2637.0 2.430 1337.8 2.380 1342.8 2.113 1343.8 2.067 947.8 1.903 955.8 1.647 9______________________________________ *peak from tridynite **impurity peak
(c) The species denominated herein as CoAPSO-5 has a three-dimensional microporous crystal framework structure of CoO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" are the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table IX-A:
TABLE IX-A______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________7.3-7.5 12.11-11.79 m-vs14.7-14.9 6.03-5.95 w-m19.6-19.8 4.53-4.48 w-m20.9-21.2 4.25-4.19 w-vs22.3-22.4 3.99-3.97 m-vs25.8-26.0 3.453-3.427 vw-m______________________________________
(d) The CoAPSO-5 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table X-A:
TABLE X-A______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________7.3-7.5 12.11-11.79 32-10012.7-12.9 6.97-6.86 2-2214.7-14.9 6.03-5.95 10-2619.6-19.8 4.53-4.48 7-3920.9-21.2 4.25-4.19 19-10022.3-22.4 3.99-3.97 25-9424.4-24.8 3.65-3.59 2-1625.8-26.0 3.453-3.427 6-4129.0-29.1 3.079-3.069 3-2629.9-30.1 2.988-2.969 3-3033.5-33.7 2.667-2.660 2-1334.4-34.6 2.607-2.592 4-2236.8-37.0 2.442-2.430 2-1337.5-37.8 2.398-2.380 3-1641.4-41.5 2.181-2.176 1-742.2-42.8 2.141-2.113 1-1343.7-43.8 2.071-2.067 0-944.9-45.0 2.019-2.014 1-747.5-47.8 1.914-1.903 3-1055.6-55.8 1.653-1.647 1-10______________________________________
EXAMPLE 111A
(a) The as-synthesized CoAPSO-11 of example 42A was subjected to analysis by x-ray. The CoAPSO-11 product was characterized by the x-ray powder diffraction pattern of Table XI-A below:
TABLE XI-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________7.9 11.19 329.3 9.51 7212.3* 7.20 1613.1 6.76 2415.6 5.68 3216.2 5.47 1218.2 4.87 1618.9 4.70 1220.3 4.37 4021.0 4.23 10022.1 4.02 5622.5 3.95 6022.7 3.92 7223.1 3.85 6824.6 3.62 2026.3 3.389 2828.2 3.164 1628.5 3.132 2429.4 3.038 2029.6 3.018 1629.9 2.988 1631.3 2.858 1632.6 2.747 2434.0 2.637 1636.3 2.475 1237.6 2.392 2039.3 2.292 1242.8 2.113 844.8 2.023 850.5 1.807 1254.4 1.687 12______________________________________ *peak may contain impurity
(b) CoAPSO-11, of example 42A was calcined in air at 600.degree. for 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern of Table XII-A below:
TABLE XII-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.1 10.92 709.5 9.31 8313.1 6.76 2613.5 6.56 3015.8 5.61 5618.5* 4.80 1719.2 4.62 1320.2 4.40 sh20.3 4.37 3521.3 4.17 10022.3 3.99 6122.5 3.95 sh23.0 3.87 6523.4 3.80 5224.3 3.66 1725.1 3.548 1726.5 3.363 3026.6 3.351 sh28.2 3.164 1328.9 3.089 2629.5 3.028 1730.1 2.969 1330.5 2.931 1731.8 2.814 1732.9 2.722 2234.7 2.585 1336.2 2.481 1337.9 2.374 1738.3 2.350 1739.5 2.281 9______________________________________ *peak may contain impurity
(c) The species denominated herein as CoAPSO-11 has a three-dimensional microporous crystal framework structure of CoO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIII-A:
TABLE XIII-A______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________7.9-8.1 11.19-10.92 m9.3-9.5 9.51-9.31 m-s21.0-21.3 4.23-4.17 vs22.1-22.3 4.02-3.99 m22.7-23.1 3.92-3.85 m23.2-23.4 3.83-3.80 m______________________________________
(d) The CoAPSO-11 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XIV-A:
TABLE XIV-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________7.9-8.1 11.19-10.92 32-709.3-9.5 9.51-9.31 72-8312.3* 7.20 1613.1-13.2 6.76-6.71 16-2613.5-13.6 6.56-6.51 3015.6-15.8 5.68-5.61 32-5616.2-16.3 5.47-5.44 8-1218.2-18.5 4.87-4.80 16-1718.9-19.2 4.70-4.62 12-1319.7-20.2 4.51-4.40 sh20.3 4.37 35-4021.0-21.3 4.23-4.17 10022.1-22.3 4.02-3.99 56-6122.4-22.6 3.97-3.93 sh-6022.7-23.1 3.92-3.85 65-7223.2-23.4 3.83-3.80 52-6824.3-24.6 3.66-3.62 17-2025.1 3.548 1726.3-26.5 3.389-3.363 28-3026.6 3.351 sh28.1-28.2 3.175-3.164 13-1628.5-28.9 3.132-3.089 24-2629.4-29.5 3.038-3.028 17-2029.6-30.5 3.018-2.931 13-1731.3-31.8 2.858-2.814 16-1732.6-32.9 2.747-2.722 22-2434.0-34.7 2.637-2.585 13-1636.2-36.3 2.481-2.475 12-1336.7-37.9 2.392-2.374 17-2038.3-38.4 2.350-2.344 17-1839.3-39.5 2.292-2.281 9-1242.8-42.9 2.113-2.108 8-944.7- 44.8 2.027-2.023 8-950.5-50.6 1.807-1.804 9-1254.4-54.6 1.687-1.681 9-12______________________________________ *peak may contain impurity
EXAMPLE 112-A
(a) The as-synthesized CoAPSO-16 of example 4A was subjected to analysis by x-ray. The CoAPSO-16 product was characterized by the x-ray powder diffraction pattern of Table XV-A below:
TABLE XV-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.7* 10.16 1711.0* 8.04 4011.5 7.69 3213.0* 6.81 1515.9* 5.57 1317.3* 5.13 5517.9* 4.96 1318.8 4.72 2320.8* 4.27 (sh)21.2* 4.19 4022.0** 4.04 10023.2** 3.83 2123.8* 3.74 1125.1* 3.548 926.9** 3.314 2328.6* 3.121 2628.8* 3.100 2629.0 3.079 1529.6 3.018 1129.9 2.988 1532.2* 2.780 3432.8 2.730 934.6** 2.592 1335.8* 2.508 1137.9 2.374 940.1 2.249 942.2* 2.141 1143.0* 2.103 944.5 2.036 948.6** 1.873 1349.6 1.838 1151.6 1.771 1152.6 1.740 655.0 1.670 655.4* 1.658 11______________________________________ *peak resulting from CoAPSO35 **peak resulting from CoAPSO16 and CoAPSO35
(b) The species denominated herein as CoAPSO-16 has a three-dimensional microporous crystal framework structure of CoO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XVI-A:
TABLE XVI-A______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________11.4-11.6 7.76-7.63 w-s17.2-17.4 5.16-5.10 m18.7-18.9 4.75-4.70 vw-m21.9-22.1 4.06-4.02 vs23.1-23.3 3.85-3.82 m26.8-27.0 3.326-3.302 m29.8-29.9 2.998-2.988 w-m______________________________________
(c) The CoAPSO-16 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XVII-A:
TABLE XVII-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________11.4-11.6 7.76-763 11-7917.2-17.4 5.16-5.10 66-8018.7-18.9 4.75-4.70 7-5321.9-22.1 4.06-4.02 10023.1-23.3 3.85-3.82 21-2426.8-27.0 3.326-3.302 23-2829.0 3.079 14-1829.5-29.7 3.028-3.008 4-1529.8-29.9 2.998-2.988 15-2932.7-32.9 2.739-2.722 3-934.5-34.7 2.600-2.585 9-1337.8-38.0 2.380-2.368 6-940.0-40.2 2.534-2.243 1-944.3-44.6 2.045-2.032 2-948.5-48.7 1.877-1.870 8-1349.5-49.7 1.841-1.834 8-1151.5-51.7 1.774-1.768 6-1152.5-52.7 1.743-1.737 6-754.9-55.1 1.672-1.667 1-6______________________________________
EXAMPLE 113A
(a) The as-synthesized CoAPSO-20 of example 106A was subjected to analysis by x-ray. The CoAPSO-20 product was characterized by the x-ray powder diffraction pattern of Table XVIII-A below:
TABLE XVIII-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________10.293 8.5942 712.078 7.3278 113.925 6.3595 4614.376 6.1609 218.773 4.7268 219.738 4.4977 4220.507 4.3307 322.093 4.0233 324.227 3.6735 10026.363 3.3806 326.941 3.3094 328.052 3.1808 1131.442 2.8451 1131.759 2.8175 231.980 2.7985 234.523 2.5980 1637.426 2.4029 140.075 2.2499 442.614 2.1215 447.3 1.922 451.8 1.765 8______________________________________
(b) CoAPSO-20, of example 106A was calcined in air at 500.degree. for one hour. The calcined product was characterized by the x-ray powder diffraction pattern of Table XIX-A below:
TABLE XIX-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 10.6* 8.39 7 21.1* 7.30 3 12.2* 7.24 214.0 6.33 75 14.8* 6.01 3 16.1* 5.51 219.8 4.48 3822.2 4.01 424.3 3.66 100 26.7* 3.344 3 27.6* 3.227 228.1 3.173 1421.5 2.839 13 32.2* 2.781 2 32.4* 2.764 234.6 2.593 1840.2 2.244 342.5 2.127 447.3 1.922 451.8 1.765 8______________________________________ *impurity peak
(c) The species denominated herein as CoAPSO-20 has a three-dimensional microporous crystal framework structure of CoO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XX-A:
TABLE XX-A______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________13.9-14.0 6.37-6.33 m19.7-19.8 4.51-4.48 m24.2-24.3 3.68-3.66 vs28.0-28.1 3.187-3.175 w31.4-31.5 2.849-2.840 w34.5-34.6 2.600-2.592 w______________________________________
(d) The CoAPSO-20 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXI-A:
TABLE XXI-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________13.9-14.0 6.37-6.33 44-7519.7-19.8 4.51-4.48 38-4222.1-22.2 4.02-4.00 3-424.2-24.3 3.68-3.66 10028.0-28.1 3.187-3.175 11-1431.4-31.5 2.849-2.840 11-1234.5-34.6 2.600-2.592 16-1840.1-40.2 2.249-2.243 3-442.5-42.6 2.127-2.122 3-447.3-47.4 1.922-1.918 4-551.8-51.9 1.765-1.762 8-9______________________________________
EXAMPLE 114A
(a) The as-synthesized CoAPSO-31 of example 101A was subjected to analysis by x-ray. The CoAPSO-31 product was characterized by the x-ray powder diffraction pattern of Table XXII-A below:
TABLE XXII-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 8.5 10.35 5817.1 5.19 518.4 4.82 220.3 4.38 4221.1 4.20 422.1 4.03 2822.7 3.93 10023.2 3.83 225.2 3.537 425.7 3.464 328.0 3.187 1229.8 3.000 631.8 2.816 2035.2 2.549 936.2 2.482 237.2 2.417 237.7 2.386 238.3 2.352 239.4 2.288 339.7 2.271 240.3 2.239 245.3 2.002 246.8 1.943 248.7 1.869 251.7 1.768 4______________________________________
(b) CoAPSO-31 of part (a) was calcined in air at 500.degree. for 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern of Table XXIII-A below:
TABLE XXIII-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 8.5 10.36 7314.8 5.99 417.1 5.19 1018.4 4.81 420.3 4.37 5621.4 4.15 322.1 4.03 4722.7 3.93 10023.4 3.80 325.2 3.530 625.7 3.464 728.0 3.184 1529.8 2.300 1031.0 2.885 231.8 2.813 3135.2 2.548 1036.3 2.476 537.3 2.409 337.7 2.385 338.3 2.348 339.4 2.287 439.7 2.270 340.3 2.237 346.7 1.944 547.6 1.910 348.7 1.868 349.3 1.849 251.7 1.768 6______________________________________
(c) The species denominated herein as CoAPSO-31 has a three-dimensional microporous crystal framework structure of CoO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXIV-A:
TABLE XXIV-A______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________8.5-8.6 10.40-10.28 m20.2-20.3 4.40-4.37 m22.0-22.1 4.04-4.02 m22.6-22.7 3.93-3.92 vs28.0-28.1 3.187-3.175 w31.7-31.8 2.823-2.814 m______________________________________
(d) The CoAPSO-31 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXV-A:
TABLE XXV-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.5-8.6 10.40-10.28 58-7314.7-14.8 6.03-5.99 2-417.0-17.2 5.22-5.16 5-1018.4-18.5 4.82-4.80 2-420.2-20.3 4.40-4.37 42-5621.1-21.4 4.21-4.15 3-422.0-22.1 4.04-4.02 28-4722.6-22.7 3.93-3.92 10023.2-23.4 3.83-3.80 2-325.1-25.2 3.548-3.534 4-625.7-25.8 3.466-3.453 3-728.0-28.1 3.187-3.175 12-1529.7-29.8 3.008-2.998 6-1031.0-31.1 2.885-2.876 2-431.7-31.8 2.823-2.814 20-3135.2-35.3 2.550-2.543 9-1036.2-36.3 2.481-2.475 2-537.2-37.3 2.417-2.411 2-337.7-37.8 2.386-2.380 2-338.2-38.4 2.356-2.344 2-339.3-39.4 2.292-2.287 3-439.6-39.7 2.276-2.270 2-340.2-40.3 2.243-2.238 2-345.2-45.3 2.006-2.002 1-246.7-46.8 1.945-1.941 2-547.5-47.6 1.914-1.910 2-348.7-48.8 1.870-1.866 2-349.2-49.3 1.852-1.848 1-251.6-51.7 1.771-1.768 4-6______________________________________
EXAMPLE 115A
(a) The as-synthesized CoAPSO-34 of example 90A was subjected to analysis by x-ray. The CoAPSO-34 product was characterized by the x-ray powder diffraction pattern of Table XXVI-A below:
TABLE XXVI-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 9.6 9.22 10012.9 6.84 1114.2 6.26 1016.1 5.51 3518.1 4.92 1520.7 4.29 6222.3 3.98 323.2 3.84 425.3 3.522 1726.0 3.430 1427.7 3.217 228.5 3.136 329.7 3.010 430.7 2.914 2531.3 2.855 1631.8 2.817 334.5 2.597 636.3 2.473 339.8 2.263 343.3 2.090 343.6 2.075 347.6 1.911 247.8 1.904 349.2 1.853 551.1 1.786 353.4 1.716 354.7 1.678 2______________________________________
(b) CoAPSO-34, of example 90A was calcined in air at 600.degree. for 1 hour. The calcined product was characterized by the x-ray powder diffraction pattern of Table XXVII-A below:
TABLE XXVII-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 9.6 9.20 10010.1 8.77 613.0 6.80 1416.2 5.46 817.9 4.97 418.0 4.94 319.3 4.60 420.5 4.34 320.8 4.27 1421.4 4.15 423.3 3.82 224.3 3.67 325.1 3.543 325.3 3.524 325.7 3.464 226.2 3.402 531.0 2.831 1031.6 2.835 531.8 2.815 3______________________________________
(c) The species denominated herein as CoAPSO-34 has a three-dimensional microporous crystal framework structure of CoO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions, being as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXVIII-A:
TABLE XXVIII-A______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________9.4-9.8 9.41-9.03 s-vs12.86-13.06 6.86-6.76 w14.08-14.30 6.28-6.19 w-m15.90-16.20 5.57-5.47 vw-m20.60-20.83 4.31-4.26 w-vs30.50-30.80 2.931-2.903 w-m______________________________________
(d) The CoAPSO-34 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXIX-A:
TABLE XXIX-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________9.4-9.8 9.41-9.03 87-10010.09-10.14 8.77-8.72 1-612.86-13.06 6.86-6.76 11-1814.08-14.30 6.28-6.19 10-2415.90-16.24 5.57-5.47 8-3517.85-18.05 4.97-4.92 3-1519.13-19.48 4.65-4.55 1-420.48-20.56 4.34-4.33 sh-320.60-20.83 4.31-4.26 14-10021.41-22.35 4.15-3.98 3-423.18-23.31 3.84-3.82 2-324.25-24.53 3.67-3.63 0-325.13-25.29 3.543-3.520 3-1725.72-25.98 3.464-3.430 3-1426.06-26.19 3.414-3.402 5-927.73-27.80 3.217-3.209 2-1628.30-28.46 3.153-3.136 3-929.50-29.68 3.028-3.010 4-1430.50-30.80 2.931-2.903 12-2531.04-31.33 2.881-2.855 7-1631.60-31.79 2.831-2.815 3-534.40-34.53 2.607-2.597 5-636.20-36.32 2.481-2.473 3-838.40-38.60 2.344-2.332 3-539.70-39.83 2.270-2.263 3-443.10-43.28 2.099-2.090 sh-643.40-43.61 2.045-2.075 3-1047.40-47.59 1.918-1.911 sh-247.77- 47.80 1.904-1.903 3-1049.17-49.20 1.853-1.852 5-1049.90-50.40 1.828-1.809 0-1151.13-51.20 1.786-1.784 3-1053.20-53.39 1.722-1.716 3-1054.60-54.70 1.681-1.678 2-755.80-55.90 1.647-1.645 2-10______________________________________
EXAMPLE 116A
(a) The as-synthesized CoAPSO-35 of example 10A was subjected to analysis by x-ray. The CoAPSO-35 product was characterized by the x-ray powder diffraction pattern of Table XXX-A below:
TABLE XXX-a______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 7.9* 11.19 8 8.6 10.28 1810.9 8.12 4511.6 7.63 813.4 6.61 3015.9 5.57 1517.3 5.13 8317.8 4.98 2020.9 4.25 5821.9 4.06 10022.7 3.92 1323.3 3.82 3824.9 3.58 1325.6 3.480 826.9 3.314 2828.3 3.153 4529.1 3.069 13 31.4* 2.849 1032.2 2.780 4034.3 2.614 10 35.2* 2.550 835.9 2.501 837.8 2.380 539.4 2.287 541.9 2.156 842.6 2.122 1044.6 2.032 847.8 1.903 848.6 1.873 849.8 1.831 1051.2 1.784 1055.7 1.650 8______________________________________ *impurity peak
(b) CoAPSO-35, of example 10A was calcined in air at 500.degree. C. for two hours. The calcined product was characterized by the x-ray powder diffraction pattern of Table XXXI-A below:
TABLE XXXI-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 8.7 10.16 2611.0 8.04 9011.8 7.50 2113.7 6.46 10016.2 5.47 1617.4 5.10 2617.6 5.04 3721.2 4.19 4222.3 3.99 5823.2 3.83 2623.7 3.75 3725.1 3.548 2625.3 3.520 3226.3 3.389 2627.5 3.243 4228.6 3.121 5328.8 3.100 5329.6 3.018 32 31.9* 2.805 2632.8 2.730 4234.5 2.600 2135.0 2.564 2135.8 2.508 16______________________________________ *impurity peak
(c) The species denominated herein as CoAPSO-35 has a three-dimensional microporous crystal framework structure of CoO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXXII-A:
TABLE XXXII-A______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________10.9-11.0 8.12-8.04 m-vs13.4-13.7 6.61-6.46 m-vs17.3-17.4 5.13-5.10 m-s20.9-21.2 4.25-4.19 m21.9-22.3 4.06-3.99 m-s28.3-28.6 3.153-3.121 m______________________________________
(d) The CoAPSO-35 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXXIII-A:
TABLE XXXIII-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________7.9* 11.19 88.6-8.7 10.28-10.16 18-2610.9-11.0 8.12-8.04 45-9011.6-11.8 7.63-7.50 8-2113.4-13.7 6.61-6.46 30-10015.9-16.2 5.57-5.47 15-1617.3-17.4 5.13-5.10 26-8317.6-17.8 5.04-5.98 20-3720.9-21.2 4.25-4.19 42-5821.9-22.3 4.06-3.99 58-10022.7-23.2 3.92-3.83 13-2623.3-23.7 3.83-3.75 37-3824.9-25.1 3.58-3.548 13-2625.3 3.520 3225.6-26.3 3.480-3.389 8-2626.9-27.5 3.314-3.243 28-4228.3-28.6 3.153-3.121 45-5328.8-29.6 3.100-3.018 13-5331.4-31.9 2.849-2.805 10-2632.2-32.8 2.780-2.730 40-4234.3-34.5 2.614-2.600 10-21 35.0-35.2* 2.564-2.550 8-2135.8-35.9 2.508-2.501 8-1637.8-37.9 2.380-2.374 539.4-39.5 2.287-2.281 541.9-42.0 2.156-2.151 842.6-42.7 2.122-2.118 1044.6-44.7 2.032-2.027 847.8-47.9 1.903-1.900 848.6-48.7 1.873-1.870 849.8-49.9 1.831- 1.828 1051.2-51.3 1.784-1.781 1055.6-55.7 1.653-1.650 8______________________________________
EXAMPLE 117A
(a) The as-synthesized CoAPSO-36 of example 93A was subjected to analysis by x-ray. The CoAPSO-36 product was characterized by the x-ray powder diffraction pattern of Table XXXIV-A below:
TABLE XXXIV-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 7.3 12.11 7 8.0 11.12 100 8.2 10.74 29 9.2 9.65 412.9 6.86 513.6 6.52 813.7 6.48 815.9 5.57 1416.5 5.38 4218.4 4.83 619.1 4.64 3720.8 4.27 4921.6 4.12 721.8 4.09 2222.1 4.03 2822.6 3.94 2923.0 3.86 924.0 3.71 927.3 3.267 2027.7 3.226 728.4 3.148 1328.7 3.116 529.2 3.063 1230.4 2.940 732.1 2.792 1234.9 2.571 12______________________________________
(b) CoAPSO-36, of example 93A was calcined in air at 500.degree. for one hour. The calcined product was characterized by the x-ray powder diffraction pattern of Table XXXV-A below:
TABLE XXXV-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 7.4 12.00 8 8.0 11.10 100 8.3 10.69 3313.6 6.52 1315.9 5.58 816.6 5.36 3219.3 4.59 2920.8 4.27 2621.5 4.14 821.8 4.07 1122.3 3.98 1922.7 3.92 1724.0 3.71 727.3 3.266 1927.3 3.215 1028.8 3.154 1228.4 3.145 1328.5 3.131 1029.2 3.062 1332.0 2.797 10______________________________________
(c) The species denominated herein as CoAPSO-36 has a three-dimensional microporous crystal framework structure of CoO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXXVI-A:
TABLE XXXVI-A______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________7.8-8.0 11.33-11.05 vs8.2-8.3 10.78-10.65 m16.4-16.6 5.40-5.34 m19.0-19.3 4.67-4.60 m20.7-21.0 4.29-4.23 m22.3-22.6 3.99-3.93 w-m______________________________________
(d) The CoAPSO-36 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXXVII-A:
TABLE XXXVII-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________7.3-7.5 12.11-11.79 7-87.8-8.0 11.33-11.05 1008.2-8.3 10.78-10.65 29-339.2-9.3 9.61-9.51 4-512.9-13.0 6.86-6.81 4-513.5-13.6 6.56-6.51 8-1313.7 6.46 7-815.8-16.0 5.61-5.54 8-1416.4-16.6 5.40-5.34 32-4218.4 4.82 4-619.0-19.3 4.67-4.60 29-3620.7-21.0 4.29-4.23 26-4921.5-21.7 4.13-4.10 7-821.8-22.0 4.08-4.04 11-2222.3-22.6 3.99-3.93 17-2922.9-23.0 3.88-3.87 5-923.9-24.0 3.72-3.71 7-927.2-27.3 3.278-3.267 19-2027.6-27.8 3.232-3.209 7-1028.3-28.4 3.153-3.143 12-1328.5-28.7 3.132-3.110 5-1029.0-29.2 3.079-3.058 12-1330.3-30.4 2.950-2.940 5-732.0-32.1 2.797-2.788 10-1234.7-34.9 2.585-2.571 10-12______________________________________
EXAMPLE 118A
(a) The as-synthesized CoAPSO-39 of example 45A was subjected to analysis by x-ray. The CoAPSO-39 product was characterized by the x-ray powder diffraction pattern of Table XXXVIII-A below:
TABLE XXXVIII-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.0* 11.05 319.4** 9.41 4713.1* 6.76 2213.3 6.66 1614.8* 5.99 915.6* 5.68 3116.2* 5.47 618.1 4.90 1619.0* 4.67 920.2* 4.40 4121.0** 4.23 10022.1* 4.02 5322.4** 3.97 5322.6* 3.93 6923.1* 3.85 6624.7* 3.60 1326.4** 3.376 2826.9 3.314 1327.7* 3.220 1328.1 3.175 1328.6** 3.121 2529.4 3.038 1330.2 2.959 1331.4* 2.849 1332.7** 2.739 2234.2** 2.622 1634.6 2.592 636.2 2.481 637.6 2.392 1637.8** 2.380 1639.4** 2.287 942.9** 2.108 944.6** 2.032 948.6 1.873 650.6* 1.804 651.4 1.778 654.5** 1.684 955.6** 1.653 6______________________________________ *peak resulting from CoAPSO11 **peak resulting from CoAPSO11 and CoAPSO 39
(b) The species denominated herein as CoAPSO-39 has a three-dimensional microporous crystal framework structure of CoO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXXIX-A:
TABLE XXXIX-A______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________9.4-9.5 9.41-9.31 m13.3-13.4 6.66-6.61 m18.1-18.2 4.90-4.87 w-m21.0-21.2 4.23-4.19 vs22.4-22.5 3.97-3.95 m-s26.4-26.5 3.376-3.363 m______________________________________
(c) The CoAPSO-39 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXXX-A:
TABLE XXXX-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________9.4-9.5 9.41-9.31 31-4313.3-13.4 6.66-6.61 22-3018.1-18.2 4.90-4.87 16-3121.0-21.2 4.23-4.19 10022.4-22.5 3.97-3.95 53-8026.4-26.5 3.376-3.363 28-2926.9-27.0 3.314-3.302 6-1328.1-28.2 3.175-3.164 13-1528.6-28.7 3.121-3.11 10-2529.4-29.5 3.038-3.028 13-1830.2 2.959 13-1532.7-32.8 2.739-2.730 17-2234.2-34.3 2.622-2.614 12-1634.5-34.6 2.617-2.592 6-1036.2-36.3 2.481-2.475 6-837.6-37.9 2.392-2.374 16-1739.4-39.5 2.287-2.281 9-1142.9-43.0 2.108-2.103 8-944.6-44.8 2.032-2.023 6-948.5-48.6 1.877-1.873 5-651.4-51.6 1.778-1.771 5-654.5-54.6 1.684-1.681 9-1055.4-55.6 1.658-1.653 5-6______________________________________
EXAMPLE 119A
(a) The as-synthesized CoAPSO-44 of example 19A was subjected to analysis by x-ray. The CoAPSO-44 product was characterized by the x-ray powder diffraction pattern of Table XXXXI-A below:
TABLE XXXXI-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________4.8* 18.41 89.4 9.41 10013.1 6.76 2213.9 6.37 515.9 5.57 (sh)16.2 5.47 3717.4 5.10 519.0 4.67 920.8 4.27 7221.8 4.08 1722.7 3.92 923.1 3.85 924.4 3.65 4926.2 3.401 3127.8 3.209 1129.0 3.079 sh29.7 3.008 830.1 2.969 2030.8 2.903 4931.6 2.831 332.5 2.755 632.9 2.722 634.8 2.578 535.5 2.529 938.6 2.332 539.3 2.292 339.8 2.265 sh40.0 2.254 642.2 2.141 542.6 2.122 543.7 2.071 344.4 2.040 346.2 1.965 347.3 1.922 348.2 1.888 1248.7 1.870 850.3 1.814 1552.0 1.759 553.8 1.704 954.8 1.675 3______________________________________
(b) CoAPSO-44 of example 19A was calcined in air at 500.degree. for 1.25 hours. The calcined product was characterized by the x-ray powder diffraction pattern of Table XXXXII-A below:
TABLE XXXXII-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.9 9.94 209.3 9.51 10012.9 6.86 2414.0 6.33 515.8 5.61 sh16.0 5.54 1417.8 4.98 1819.1 4.65 420.5 4.33 4022.1 4.02 422.3 3.99 423.0 3.87 725.1 3.548 1225.8 3.453 1327.6 3.232 328.2 3.164 429.5 3.028 330.6 2.921 2131.1 2.876 1431.7 2.823 432.2 2.780 233.4 2.683 333.7 2.660 434.5 2.600 836.2 2.481 538.2 2.356 238.7 2.327 339.2 2.298 239.8 2.265 342.9 2.108 343.4 2.085 447.6 1.910 349.0 1.859 549.8 1.831 350.6 1.804 351.0 1.791 453.2 1.722 354.7 1.678 2______________________________________
(c) The species denominated herein as CoAPSO-44 has a three-dimensional microporous crystal framework structure of CoO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXXXIII-A:
TABLE XXXXIII-A______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________9.3-9.5 9.51-9.31 vs16.0-16.3 5.54-5.44 w-m20.5-20.8 4.33-4.27 m24.3-25.1 3.66-3.548 w-m25.8-26.2 3.453-3.401 w-m30.7-31.1 2.912-2.876 vw-m______________________________________
(d) The CoAPSO-44 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXXXIV-A:
TABLE XXXXIV-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________4.8* 18.41 88.9 9.94 209.3-9.5 9.51-9.31 10012.9-13.1 6.86-6.76 22-2413.7-14.0 6.46-6.33 5-615.8-15.9 5.61-5.57 sh16.0-16.3 5.54-5.44 14-3717.4-17.8 5.10-4.98 5-1818.9-19.1 4.70-4.65 4-920.5-20.8 4.33-4.27 40-7221.8-22.1 4.08-4.02 4-1722.3-22.7 3.99-3.92 4-923.0-23.1 3.87-3.85 7-924.3-25.1 3.66-3.548 12-4925.8-26.2 3.453-3.401 13-3127.6-27.8 3.232-3.209 3-1128.2 3.164 429.0-29.5 3.079-3.028 sh-329.7-30.6 3.008-2.921 8-2130.7-31.1 2.912-2.876 4-4931.6-31.7 2.831-3.823 3-432.2 2.780 232.5-33.7 2.755-2.660 3-634.5-34.8 2.600-2.578 5-835.4-36.2 2.536-2.481 5-938.2-38.6 2.356-2.332 2-538.7-39.3 2.327-2.292 2-339.8-40.0 2.265-2.254 sh-342.2-42.9 2.141-2.108 3-543.4-43.7 2.085-2.071 3-444.4-46.2 2.040-1.965 347.3-47.6 1.922-1.910 348.1-49.0 1.892-1.859 5-1249.8-50.3 1.831-1.814 3-1550.6 1.804 351.0-52.0 1.791-1.759 4-553.2-53.8 1.722-1.704 3-954.7-54.8 1.678-1.675 2-3______________________________________
EXAMPLE 120A
(a) The as-synthesized CoAPSO-46 of example 36 was subjected to analysis by x-ray. The CoAPSO-46 product was characterized by the x-ray powder diffraction pattern of Table XXXXV-A below:
TABLE XXXXV-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________6.6 13.39 116.9 12.81 77.2 12.28 127.7 11.48 10012.5 7.08 713.1 6.76 513.3 6.66 613.5 6.56 415.0 5.91 415.4 5.75 516.1 5.51 316.8 5.28 617.4 5.10 417.5 5.07 519.9 4.46 520.6 4.31 521.0 4.23 421.4 4.15 sh21.7 4.10 1322.2 4.00 322.9 3.88 723.8 3.74 424.3 3.66 526.3 3.389 326.9 3.314 727.8 3.209 1028.3 3.153 528.8 3.010 629.9 2.988 430.2 2.959 430.7 2.912 430.9 2.894 431.2 2.867 531.8 2.814 333.0 2.714 434.2 2.622 336.0 2.495 536.6 2.455 344.0 2.058 3______________________________________
(b) The species denominated herein as CoAPSO-46 has a three-dimensional microporous crystal framework structure of CoO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXXXVI-A:
TABLE XXXXVI-A______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________6.5-6.7 13.60-13.19 w7.2-7.4 12.28-11.95 w7.6-7.8 11.63-11.33 vs21.6-21.7 4.11-4.10 w27.8-27.9 3.209-3.198 w______________________________________
(c) The CoAPSO-46 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table XXXXVII-A:
TABLE XXXXVII-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________6.5-6.7 13.60-13.19 116.9-7.0 12.81-12.63 77.2-7.4 12.28-11.95 127.6-7.8 11.63-11.33 10012.5-12.6 7.08-7.03 713.1-13.3 6.76-6.66 513.5-13.9 6.56-6.37 415.0-15.1 5.91-5.87 415.4 5.75 516.1 5.51 316.7-16.8 5.31-5.28 617.4-17.5 5.10-5.07 419.9-20.0 4.46-4.44 520.5-20.6 4.33-4.31 521.0 4.23 421.4 4.15 sh21.6-21.7 4.11-4.10 1322.1-22.2 4.02-4.00 322.8-22.9 3.90-3.88 723.8 3.74 424.2-24.3 3.68-3.66 526.3-26.4 3.389-3.376 326.8-26.9 3.326-3.314 727.8-27.9 3.209-3.198 1028.3-28.4 3.153-3.143 528.8-28.9 3.010-3.089 629.8-29.9 2.998-2.988 430.2 2.959 430.7 2.912 430.9-31.0 2.894-2.885 431.2-31.3 2.867-2.858 531.8-31.9 2.814-2.805 332.8-33.0 2.730-2.714 434.2-34.3 2.622-2.614 335.9-36.0 2.510-2.495 536.5-36.6 2.462-2.455 344.0-44.1 2.058-2.053 3______________________________________
EXAMPLE 121A
(a) The as-synthesized CoAPSO-47 of example 104A was subjected to analysis by x-ray. The CoAPSO-47 product was characterized by the x-ray powder diffraction pattern of Table XXXXVIII-A below:
TABLE XXXXVIII-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 9.4 9.37 9412.9 6.88 1613.8 6.40 916.0 5.55 4017.5 5.06 1418.9 4.69 620.6 4.32 10021.8 4.08 1122.4 3.97 423.0 3.87 1224.6 3.62 3825.9 3.443 2227.6 3.230 1129.5 3.030 630.6 2.926 4231.5 2.844 333.1 2.707 334.5 2.602 935.7 2.518 738.4 2.345 439.6 2.275 442.5 2.128 447.6 1.910 448.5 1.877 1150.3 1.815 752.3 1.749 253.2 1.721 553.9 1.700 354.3 1.690 3______________________________________
(b) CoAPSO-47, of example 104A was calcined in air at 500.degree. for 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern of Table XXXXIX-A below:
TABLE XXXXIX-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 9.6 9.18 100 3.1 6.77 2614.2 6.23 316.3 5.44 1018.1 4.90 1619.4 4.58 321.0 4.24 2622.5 3.96 323.5 3.79 325.5 3.499 1126.4 3.381 928.7 3.113 431.2 2.868 1431.7 2.824 6______________________________________
(c) The species denominated herein as CoAPSO-47 has a three-dimensional microporous crystal framework structure of CoO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units and has an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
where "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" per mole of (Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero to about 0.3; "w", "x", "y" and "z" represent the mole fractions as above defined with reference to FIG. 1 or FIG. 2; and having in the as-synthesized or calcined form a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table LI-A:
TABLE LI-A______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________9.4-9.6 9.41-9.21 vs12.8-13.1 6.92-6.76 w-m16.0-16.3 5.54-5.44 w-m20.6-21.0 4.31-4.23 m-vs25.5-25.9 3.493-3.440 w-m30.6-31.1 2.921-2.876 w-m______________________________________
(d) The CoAPSO-47 compositions for which x-ray powder diffraction patterns have been obtained to date have patterns which are characterized by the x-ray pattern of Table LII-A:
TABLE LII-A______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________9.4-9.6 9.41-9.21 94-10012.8-13.1 6.92-6.76 16-2613.8-14.2 6.42-6.24 3-916.0-16.3 5.54-5.44 10-4017.5-18.1 5.07-4.90 14-1618.9-19.4 4.70-4.58 3-620.6-21.0 4.31-4.23 26-10021.8 4.08 1122.4-22.5 3.97-3.95 3-423.0-23.5 3.87-3.79 3-1224.6 3.62 3825.5-25.9 3.493-3.440 11-2226.4 3.376 927.6 3.232 1128.7 3.110 429.5 3.028 630.6-31.1 2.921-2.876 13-4231.5-31.7 2.840-2.823 3-633.1 2.706 334.5 2.600 935.7 2.515 738.4 2.344 439.6 2.276 442.5 2.127 447.6 1.910 448.5 1.877 1150.3 1.814 752.3 1.749 253.2 1.722 553.9 1.701 354.3 1.689 3______________________________________
EXAMPLE 122A
In order to demonstrate the catalytic activity of the CoAPSO compositions, calcined samples of the CoAPSO products were tested for catalytic cracking by n-butane cracking.
The n-butane cracking was carried out using a bench scale rector. The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm. I.D. In each test the reactor was loaded with particles of the test CoAPSO's which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. Most of the CoAPSO had been previously calcined in air to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500.degree. C. for one hour. In some instances, samples were calcined in situ. The feedstock was a helium-n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.
The pseudo-first-order rate constant (k.sub.A) was calculated to determine the relative catalytic activity of the CoAPSO compositions. The k.sub.A value (cm.sup.3 /g min) obtained for the CoAPSO compositions are set forth, below.
______________________________________CoAPSOof Example No: Rate Constant (k.sub.A)______________________________________CoAPSO-11 (Ex. 50A) 1.0CoAPSO-11 (Ex. 42A)* 2.0CoAPSO-11 (Ex. 42A) 1.9CoAPSO-11 (Ex. 61A) 1.4CoAPSO-31 (Ex. 102A) 2.1CoAPSO-34 (Ex. 89A)* 1.5CoAPSO-34 (Ex. 89A) 8.7CoAPSO-34 (Ex. 90A) 11.8CoAPSO-34 (Ex. 83A) 28.1CoAPSO-34 (Ex. 77A)* 11.1CoAPSO-35 (Ex. 10A)* 1.0CoAPSO-44 (Ex. 19A) 18.1CoAPSO-46 (Ex. 36A) 2.4CoAPSO-47 (Ex. 104A) 2.3CoAPSO-44 (Ex. 19A)* 2.7CoAPSO-36 (Ex. 93A)* 1.0CoAPSO-34 (Ex. 83A)* 4.1CoAPSO-34 (Ex. 69A)* 9.4CoAPSO-34 (Ex. 79A)* 5.2CoAPSO-34 (Ex. 78A)* 4.6CoAPSO-34 (Ex. 81A)* 3.3______________________________________ *calcined in situ at 500.degree. C. in helium for 2 hours prior to activation.
MAGNESIUM-ALUMINUM-PHOSPHORUS-SILICON OXIDE MOLECULAR SIEVES
Molecular sieves containing magnesium, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents
In the following examples the MgAPSO compositions were prepared using numerous reagents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:
(a) Alipro: aluminum isoproproxide;
(b) CATAPAL: Trademark of Condea for hydrated pseudo-boehmite;
(c) LUDOX LS: Trademark of DuPont for an aqueous solution of 30 weight percent SiO.sub.2 and 0.1 weight percent Na.sub.2 O;
(d) Mg(Ac).sub.2 : magnesium acetate tetrahydrate, Mg(C.sub.2 H.sub.3 O.sub.2).4H.sub.2 O;
(e) H.sub.3 PO.sub.4 : 85 weight percent phosporic acid in water;
(f) TBAOH: tetrabutylammonium hydroxide (40 wt. % in water);
(g) Pr.sub.2 NH: di-n-propylamine;
(h) Pr.sub.3 N: tri-n-propylamine;
(i) Quin: Quinuclidine;
(j) MQuin: Methyl Quinuclidine hydroxide (17.9% in water);
(k) C-hex; cyclohexylamine;
(l) TEAOH: tetraethylammonium hydroxide (40 wt. % in water).
(m) DEEA: diethylethanolamine;
(n) i-Pr.sub.2 NH: di-isopropylamine;
(o) TEABr: tetraethylammonium bromide; and
(p) TPAOH: tetrapropylammonium hydroxide (40 wt. % in water).
Preparative Procedure
The MgAPSO compositions were prepared by preparing reaction mixtures having a molar composition expressed as:
eR:fMgO:hAl.sub.2 O.sub.3 :iP.sub.2 O.sub.5 :gSiO.sub.2 :jH.sub.2 O
wherein e, f, g, h, i and j represent the moles of template R, magnesium (expressed as the oxide), SiO.sub.2, Al.sub.2 O.sub.3, P.sub.2 O.sub.5 (H.sub.3 PO.sub.4 expressed as P.sub.2 O.sub.5) and H.sub.2 O, respectively. The values for e, f, g, h, i and j were as set forth in the hereinafter discussed preparative examples.
The reaction mixtures were prepared by three procedures, designated hereinafter as Methods A, B and C, unless otherwise noted in the preparative examples.
Method A was employed for examples 1B to 25B, 27B-30B, 39B-46B, 55B-57B, 61B, 63B-71B, 77B-85B and 87B-106B. Method B was employed for examples 31B-38B and 47B-54B. Method C was employed for examples 26B, 62B and 72-76B. The aluminum source was aluminum iso-propoxide except that CATAPAL was the aluminum source in examples 39B-55B and 58B-61B.
METHOD A
The reaction mixture was prepared by mixing the ground aluminum source (Al-ipro or CATAPAL) with the H.sub.3 PO.sub.4 and water on a gradual basis with occasional cooling with an ice bath. The resulting mixture was blended until a homogeneous mixture was observed. When the aluminum source was CATAPAL the water and H.sub.3 PO.sub.4 were first mixed and the CATAPAL added thereto. The magnesium acetate was dissolved in portion of the water and was then added followed by addition of the LUDOX-LS. The combined mixture was blended until a homogenous mixture was observed. The organic templating agent was added to this mixture and blended until a homogenous mixture was observed. The resulting mixture (final reaction mixture) was placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150.degree. C. or 200.degree. C.) for an effective time. Alternatively, if the digestion temperature was 100.degree. C. the final reaction mixture was placed in a lined (polytetrafluoroethylene) screw top bottle for a time. All digestions were carried out at the autogeneous pressure. The products were removed from the reaction vessel cooled and evaluated as set forth hereinafter.
METHOD B
When method B was employed the organic templating agent was di-n-propylamine. The aluminum source, silicon source and one-half of the water were first mixed and blended until a homogeneous mixture was observed. A second solution was prepared by mixing the remaining water, the H.sub.3 PO.sub.4 and the magnesium acetate. This solution was then added to the above mixture. The magnesium acetate and H.sub.3 PO.sub.4 solution was then added to the above mixture and blended until a homogeneous mixture was observed. The organic templating agent(s) was then added and the resulting reaction mixture digested and product recovered as was done in Method A.
METHOD C
Method C was carried out by mixing aluminum isopropoxide, LUDOX LS and water in a blender or by mixing water and aluminum iso-propoxide in a blender followed by addition of the LUDOX LS. H.sub.3 PO.sub.4 and magnesium acetate were then added to this mixture. The organic templating agent was then added to the resulting mixture and digested and product recovered as was done in Method A.
The following examples are provided to further illustrate the invention and are not intended to be limiting thereof.
EXAMPLES 1B TO 90B AND AB TO QB
MgAPSO molecular sieves were prepared according to the above described Methods A, B and C by preparing reaction mixtures expressed as
eR:fMgO:hAl.sub.2 O.sub.3 :iP.sub.2 O.sub.5 :gSiO.sub.2 :jH.sub.2 O
wherein, e, f, h, i, g and j represent the moles of template R, magnesium (expressed as the oxide), Al.sub.2 O.sub.3, SiO.sub.2, P.sub.2 O.sub.5 (H.sub.3 PO.sub.3 expressed as P.sub.2 O.sub.5), and H.sub.2 O respectively. The values for e, f, g, h and i for examples 1B to 90B are set forth in Table I-B to VI-B. The value of "j" was 50 in examples 1B to 84B and 87B-90B and was 75B in example 85B and was 71B in example 86B. Tables IB to VI-B also shows the temperature (.degree.C.) and time (hours) employed for digestion and indicates the final MgAPSO(s) formed.
Examples AA to QB represent reaction mixtures wherein crystalline MgAPSO products were not observed when the reaction products were subjected to X-ray analysis. The results of Examples AB to QB are set forth in Table VII-B.
TABLE I-B__________________________________________________________________________ MgAPSOExample Template e f h i g Temp(.degree.C.) Time(hrs) Product(s).sup.2__________________________________________________________________________ 1B Pr.sub.3 N 1.0 0.2 0.9 0.9 0.2 150 48 MgAPSO-5; MgAPSO-36 2B Pr.sub.3 N 1.0 0.2 0.9 0.9 0.2 150 166 MgAPSO-5; MgAPSO-36 3B Pr.sub.3 N 1.0 0.2 0.9 0.9 0.2 200 48 MgAPSO-5; MgAPSO-36 4B Pr.sub.3 N 1.0 0.2 0.9 0.9 0.6 200 166 MgAPSO-5; MgAPSO-36 5B.sup.1,3 Pr.sub.3 N 1.0 0.2 0.9 0.9 0.6 150 88 MgAPSO-36; MgAPSO-5 6B.sup.1,3 Pr.sub.3 N 1.0 0.2 0.9 0.9 0.6 200 88 MgAPSO-36; MgAPSO-5 7B.sup.3 Pr.sub.3 N 1.5 0.2 0.9 0.9 0.6 150 48 MgAPSO-5; MgAPSO-36 8B.sup.3 Pr.sub.3 N 1.5 0.2 0.9 0.9 0.6 150 160 MgAPSO-5; MgAPSO-36 9B.sup.3 Pr.sub.3 N 1.5 0.9 0.9 0.9 0.6 200 48 MgAPSO-5; MgAPSO-3610B.sup.3 Pr.sub.3 N 1.5 0.2 0.9 0.9 0.6 200 160 MgAPSO-5; MgAPSO-3611B.sup.3 TPAOH 1.0 0.2 0.9 0.9 0.6 150 48 MgAPSO-5;12B.sup.3 TPAOH 1.0 0.2 0.9 0.9 0.6 150 112 MgAPSO-5;13B.sup.3 TPAOH 1.0 0.2 0.9 0.9 0.6 200 48 MgAPSO-5; MgAPSO-3614B.sup.3 TPAOH 1.0 0.2 0.9 0.9 0.6 200 112 MgAPSO-5; MgAPSO-36__________________________________________________________________________ .sup.1 Seed crystal of MAPO36 employed, as disclosed in copending U.S. Ser. No. 514,334. .sup.2 Major species as identified by xray diffraction pattern of product except that when two or more species were identified the species are listed in the order of their predominance in the MgAPSO products. .sup.3 LUDOX-LS was added before the magnesium acetate in these example.
TABLE II-B__________________________________________________________________________ MgAPSOExample Template e f h i g Temp(.degree.C.) Time(hrs) Product(s).sup.1__________________________________________________________________________.sup. 15B.sup.2 DEEA 1.0 0.2 0.9 0.9 0.6 150 88 MgAPSO-5; MgAPSO-47.sup. 16B.sup.2 DEEA 1.0 0.2 0.9 0.9 0.6 200 88 MgAPSO-5; MgAPSO-4717B Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 150 48 MgAPSO-11; MgAPSO-5;18B Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 150 166 MgAPSO-11; MgAPSO-5; MgAPSO-39; MgAPSO-4619B Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 200 48 MgAPSO-5; MgAPSO-11; MgAPSO-3920B Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 200 166 MgAPSO-11; MgAPSO-39; MgAPSO-521B Pr.sub.2 NH 1.0 0.1 0.95 0.8 0.4 125 300 MgAPSO-1122B Pr.sub.2 NH 1.0 0.1 0.95 0.8 0.4 150 47 MgAPSO-39; MgAPSO-11; MgAPSO-46; MgAPSO-3123B Pr.sub.2 NH 1.0 0.1 0.95 0.8 0.4 150 165 MgAPSO-39; MgAPSO-46; MgAPSO-11; MgAPSO-3124B Pr.sub.2 NH 1.0 0.1 0.95 0.8 0.4 200 47 MgAPSO-11; MgAPSO-5; MgAPSO-39; MgAPSO-3125B Pr.sub.2 NH 1.0 0.1 0.95 0.8 0.4 200 165 MgAPSO-11; MgAPSO-5; MgAPSO-4626B Pr.sub.2 NH 1.0 0.4 1.0 1.0 0.4 150 182 MgAPSO-46.sup. 27B.sup.2 Pr.sub.2 NH 2.0 0.9 0.9 0.2 0.2 150 96 MgAPSO-46.sup. 28B.sup.2 Pr.sub.2 NH 2.0 0.9 0.9 0.2 0.2 150 238 MgAPSO-46; MgAPSO-11.sup. 29B.sup.2 Pr.sub.2 NH 2.0 0.9 0.9 0.2 0.2 200 96 MgAPSO-11; MgAPSO-46; MgAPSO-39__________________________________________________________________________ .sup.1 Major species as identified by xray diffraction pattern of product except that when two or more species were identified the species are listed in the order of their predominance in the MgAPSO products. .sup.2 LUDOX-LS was added before magnesium acetate in these examples.
TABLE III-B__________________________________________________________________________ MgAPSOExample Template e f h i g Temp(.degree.C.) Time(hrs) Product(s).sup.1__________________________________________________________________________30B.sup.2 Pr.sub.2 NH 2.0 0.9 0.9 0.2 0.2 200 238 MgAPSO-11; MgAPSO-46; MgAPSO-39; MgAPSO-3331B.sup. Pr.sub.2 NH 1.5 0.2 0.9 0.9 0.2 150 144 MgAPSO-39; MgAPSO-11; MgAPSO-4632B.sup. Pr.sub.2 NH 1.5 0.2 0.9 0.9 0.2 200 144 MgAPSO-39; MgAPSO-11; MgAPSO-4633B.sup. Pr.sub.2 NH 1.5 0.2 0.9 0.9 0.2 150 144 MgAPSO-39; MgAPSO-11; MgAPSO-4634B.sup. Pr.sub.2 NH 1.5 0.2 0.9 0.9 0.2 200 144 MgAPSO-39; MgAPSO-11; MgAPSO-4635B.sup. Pr.sub.2 NH 1.0 0.2 2.7 0.9 0.2 150 142 MgAPSO-39; MgAPSO-1136B.sup. Pr.sub.2 NH 1.0 0.2 2.7 0.9 0.2 200 142 MgAPSO-11; MgAPSO-39; MgAPSO-4637B.sup. Pr.sub.2 NH 2.0 0.2 2.7 0.9 0.2 150 142 MgAPSO-4638B.sup. Pr.sub.2 NH 2.0 0.2 2.7 0.9 0.2 200 142 MgAPSO-4639B.sup.2 Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 150 96 MgAPSO-11; MgAPSO-39; MgAPSO-4640B.sup.2 Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 150 190 MgAPSO-11; MgAPSO-39; MgAPSO-4641B.sup.2 Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 200 96 MgAPSO-11; MgAPSO-39; MgAPSO-4642B.sup.2 Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 200 190 MgAPSO-11; MgAPSO-39; MgAPSO-4643B.sup.2 Pr.sub.2 NH 2.0 0.2 0.9 0.9 0.2 150 96 MgAPSO-46; MgAPSO-2044B.sup.2 Pr.sub.2 NH 2.0 0.2 0.9 0.9 0.2 150 190 MgAPSO-4645B.sup.2 Pr.sub.2 NH 2.0 0.2 0.9 0.9 0.2 200 96 MgAPSO-39; MgAPSO-4646B.sup.2 Pr.sub.2 NH 2.0 0.2 0.9 0.9 0.2 200 190 MgAPSO-39; MgAPSO-46__________________________________________________________________________ .sup.1 Major species as identified by xray diffraction pattern of product except that when two or more species were identified the species are listed in the order of their predominance in the MgAPSO products. .sup.2 LUDOX-LS was added before the magnesium acetate in this example.
TABLE IV-B__________________________________________________________________________ MgAPSOExample Template e f h i g Temp(.degree.C.) Time(hrs) Product(s).sup.4__________________________________________________________________________47B Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 150 94 MgAPSO-11; MgAPSO-39; MgAPSO-548B Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 150 238 MgAPSO-11; MgAPSO-39; MgAPSO-549B Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 200 94 MgAPSO-11; MgAPSO-39; MgAPSO-550B Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 200 238 MgAPSO-11; MgAPSO-5; MgAPSO-39; MgAPSO-4651B Pr.sub.2 NH 2.0 0.2 0.9 0.9 0.2 150 94 MgAPSO-46; MgAPSO-39; MgAPSO-552B Pr.sub.2 NH 2.0 0.2 0.9 0.9 0.2 150 238 MgAPSO-46; MgAPSO-11; MgAPSO-3953B Pr.sub.2 NH 2.0 0.2 0.9 0.9 0.2 200 94 MgAPSO-4654B Pr.sub.2 NH 2.0 0.2 0.9 0.9 0.2 200 238 MgAPSO-46; MgAPSO-3955B.sup.1,2 Pr.sub.2 NH 2.0 0.2 0.9 0.9 0.2 150,200 113 MgAPSO-39; MgAPSO-31; MgAPSO-1156B i-Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 150 88 MgAPSO-5; MgAPSO-11; MgAPSO-3457B i-Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 200 88 MgAPSO-5; MgAPSO-11; MgAPSO-3458B.sup.3,5 i-Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 150 96 MgAPSO-5; MgAPSO-11; MgAPSO-3959B.sup.3,5 i-Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 200 96 MgAPSO-5; MgAPSO-11; MgAPSO-3960B.sup.5 i-Pr.sub.2 NH 1.0 0.17 0.92 0.95 0.1 150 93 MgAPSO-5; MgAPSO-1161B.sup.5 i-Pr.sub.2 NH 1.0 0.17 0.92 0.95 0.1 200 93 MgAPSO-5; MgAPSO-39; MgAPSO-1162B i-Pr.sub.2 NH 1.0 0.4 1.0 1.0 0.4 150 231 MgAPSO-5; MgAPSO-11__________________________________________________________________________ .sup.1 AlPO.sub.4 -31 seed crystal .sup.2 Two mixtures were digested with one at 150.degree. C. and one at 200.degree. C. .sup.3 SAPO-11 seed crystal as disclosed in U.S. Ser. No. 400,438 .sup.4 Major species as identified by xray diffraction pattern of product except that when two or more species were identified the species are listed in the order of their predominance in the MgAPSO products. .sup.5 LUDOX-LS was added before magnesium acetate in this example.
TABLE V-B__________________________________________________________________________ MgAPSOExample Template e f h i g Temp(.degree.C.) Time(hrs) Product(s).sup.1__________________________________________________________________________63B TEAOH 1.0 0.2 0.9 0.9 0.2 150 48 MgAPSO-3464B TEAOH 1.0 0.2 0.9 0.9 0.2 150 166 MgAPSO-3465B TEAOH 1.0 0.2 0.9 0.9 0.2 200 48 MgAPSO-34; MgAPSO-566B TEAOH 1.0 0.2 0.9 0.9 0.2 200 166 MgAPSO-3467B TEAOH 1.0 0.2 0.9 0.9 0.6 150 40 MgAPSO-34; MgAPSO-568B TEAOH 1.0 0.2 0.9 0.9 0.6 150 121 MgAPSO-3469B TEAOH 1.0 0.2 0.9 0.9 0.6 200 40 MgAPSO-5; MgAPSO-3470B TEAOH 1.0 0.2 0.9 0.9 0.6 200 121 MgAPSO-5; MgAPSO-3471B TEAOH 1.0 0.2 0.9 0.9 0.6 150 114 MgAPSO-34; MgAPSO-572B TEAOH 1.0 0.4 1.0 1.0 0.4 100 111 MgAPSO-3473B TEAOH 1.0 0.4 1.0 1.0 0.4 100 182 MgAPSO-3474B TEAOH 1.0 0.4 1.0 1.0 0.4 150 111 MgAPSO-3475B TEAOH 1.0 0.4 1.0 1.0 0.4 150 182 MgAPSO-3476B TEAOH 1.0 0.4 1.0 1.0 0.4 150 231 MgAPSO-34; MgAPSO-5__________________________________________________________________________ .sup.1 Major species as identified by xray diffraction pattern of product except that when two or more species were identified the species are listed in the order of their predominance in the MgAPSO products.
TABLE VI-B__________________________________________________________________________ MgAPSOExample Template e f h i g Temp(.degree.C.) Time(hrs) Product(s).sup.1__________________________________________________________________________77B Quin 1.0 0.2 0.9 0.9 0.2 150 48 MgAPSO-35; MgAPSO-1678B Quin 1.0 0.2 0.9 0.9 0.2 150 166 MgAPSO-35; MgAPSO-1679B Quin 1.0 0.2 0.9 0.9 0.2 200 48 MgAPSO-35; MgAPSO-1680B Quin 1.0 0.2 0.9 0.9 0.2 200 166 MgAPSO-35; MgAPSO-1681B MQuin 1.0 0.2 0.9 0.9 0.2 150 40 MgAPSO-3582B MQuin 1.0 0.2 0.9 0.9 0.2 150 121 MgAPSO-3583B MQuin 1.0 0.2 0.9 0.9 0.2 200 40 MgAPSO-3584B MQuin 1.0 0.2 0.9 0.9 0.2 200 121 MgAPSO-3585B MQuin 1.0 0.2 0.9 0.9 0.6 150 114 MgAPSO-35; MgAPSO-16.sup. 86B.sup.2 TBAOH 2.0 0.4 0.8 1.0 0.4 200 48 MgAPSO-5.sup. 87B.sup.3 C-hex 1.0 0.2 0.9 0.9 0.6 150 40 MgAPSO-44; MgAPSO-5.sup. 88B.sup.3 C-hex 1.0 0.2 0.9 0.9 0.6 200 107 MgAPSO-44; MgAPSO-5.sup. 89B.sup.3 C-hex 1.0 0.2 0.9 0.9 0.6 150 40 MgAPSO-5; MgAPSO-44.sup. 90B.sup.3 C-hex 1.0 0.2 0.9 0.9 0.6 200 107 MgAPSO-5; MgAPSO-44__________________________________________________________________________ .sup.1 Major species as identified by xray diffraction pattern of product except that when two or more species were identified the species are listed in the order of their predominance in the MgAPSO products. .sup.2 The mixing order in this example was in the order of the aluminum source, magnesium source, silicon source and the phosphorus source. .sup.3 LUDOX-LS was added before magnesium acetate in this example.
TABLE VII-B.sup.1__________________________________________________________________________Example Template e f h i g j Temp(.degree.C.) Time(hrs) Method__________________________________________________________________________AB TPABr 1.0 0.4 1.0 1.0 0.4 50 150 231 CBB Pr.sub.2 NH 1.0 0.1 0.95 0.8 0.4 50 125 47 ACB Pr.sub.2 NH 1.0 0.1 0.95 0.8 0.4 50 125 165 ADB Pr.sub.2 NH 1.0 0.4 1.0 1.0 0.4 50 100 111 CEB Pr.sub.2 NH 1.0 0.4 1.0 1.0 0.4 50 100 182 CFB Pr.sub.2 NH 1.0 0.4 1.0 1.0 0.4 50 150 111 CGB Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 50 150 96 BHB Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 50 150 235 BIB Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 50 200 96 BJB Pr.sub.2 NH 1.0 0.2 0.9 0.9 0.2 50 200 235 BKB Pr.sub.2 NH 2.0 0.2 0.9 0.9 0.2 50 150 96 BLB Pr.sub.2 NH 2.0 0.2 0.9 0.9 0.2 50 150 235 BMB Pr.sub.2 NH 2.0 0.2 0.9 0.9 0.2 50 200 96 BNB Pr.sub.2 NH 2.0 0.2 0.9 0.9 0.2 50 200 235 BOB TBAOH 2.0 0.4 0.8 1.0 0.4 71 150 48 (2)PB TBAOH 2.0 0.4 0.8 1.0 0.4 71 150 160 (2)QB TBAOH 2.0 0.4 0.8 1.0 0.4 71 200 160 (2)__________________________________________________________________________ .sup.1 Reaction mixtures from which crystalline MgAPSO products were not identified by Xray analysis of the products. .sup.2 The mixing order in this example was in the order of the aluminum source, the magnesium source, the silicon source and the phosphorus source.
EXAMPLES 91B TO 106B
MgAPSO molecular sieves were prepared according to the procedures employed in examples 1B to 90B. The aluminum source was CATAPAL in examples 96B and 97B.
The results of preparative examples 91B to 106B are set forth in Table VIII-B.
TABLE VIII-B__________________________________________________________________________ MgAPSOExample.sup.2 Template e f h i g Temp(.degree.C.) Time(hrs) Product(s).sup.1__________________________________________________________________________ 91B MQuin 1.0 0.1 0.9 0.9 0.6 150 450 MgAPSO-35 92B TEAOH 1.0 0.1 0.9 0.9 0.6 150 44 MgAPSO-5; MgAPSO-34 93B TEAOH 1.0 0.1 0.9 0.9 0.6 150 44 MgAPSO-5; MgAPSO-34 94B TEAOH 1.0 0.05 1.0 1.0 0.4 100 280 MgAPSO-34 95B TEAOH 1.0 0.1 1.0 1.0 0.4 100 280 MgAPSO-34 96B Pr.sub.2 NH 2.0 0.1 0.9 0.9 0.6 150 122 MgAPSO-43; MgAPSO-46 97B Pr.sub.2 NH 2.0 0.1 0.9 0.9 0.6 150 122 MgAPSO-43; MgAPSO-46 98B Quin 1.0 0.2 0.9 0.9 0.6 220 114 MgAPSO-16; MgAPSO-35 99B C-hex 1.0 0.2 0.9 0.9 0.6 220 114 MgAPSO-44; MgAPSO-5100B TMAOH 1.0 0.2 0.9 0.7 0.6 100 18 MgAPSO-20101B TMAOH 1.0 0.2 0.9 0.7 0.6 150 111 MgAPSO-20102B TMAOH 1.0 0.2 0.9 0.7 0.6 200 22 MgAPSO-20103B TMAOH 1.0 0.2 0.9 0.7 0.6 200 111 MgAPSO-20104B DEEA 2.0 0.2 0.9 0.7 0.6 100 111 MgAPSO-47105B DEEA 2.0 0.2 0.9 0.7 0.6 100 22 MgAPSO-47; MgAPSO-5106B DEEA 2.0 0.2 0.9 0.7 0.6 100 111 MgAPSO-47__________________________________________________________________________ .sup.1 Major species as identified by xray diffraction pattern of product except that when two or more species were identified the species are listed in the order of their predominance in the MgAPSO products. .sup.2 LUDOX-LS was added before magnesium acetate in examples 91B to 106B.
EXAMPLE 107B
Samples of the MgAPSO products were subjected to chemical analysis. The chemical analysis for each of the analyzed products is given hereinafter:
(a) The chemical analysis for the MgAPSO-5 of example 4B was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 31.3P.sub.2 O.sub.5 45.4MgO 2.8SiO.sub.2 3.9Carbon 5.0LOI* 13.7______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anydrous basis) of: 0.23 MgO:1.00 Al.sub.2 O.sub.3 :1.04 P.sub.2 O.sub.5 :0.21 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.03R(Mg.sub.0.05 Al.sub.0.44 P.sub.0.46 Si.sub.0.05)O.sub.2
(b) The chemical analysis for MgAPSO-36 of example 5B was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 31.2P.sub.2 O.sub.5 44.6MgO 2.6SiO.sub.2 8.6Carbon 6.2LOI* 13.9______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.21 MgO:1.00 Al.sub.2 O.sub.3 :1.03 P.sub.2 O.sub.5 :0.45 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.04R(Mg.sub.0.05 Al.sub.0.43 P.sub.0.44 Si.sub.0.10)O.sub.2
(c) The chemical analysis for the MgAPSO-46 of example 44B was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 30.1P.sub.2 O.sub.5 38.4MgO 4.1SiO.sub.2 4.4Carbon 10.6LOI* 22.5______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.34 MgO:1.00 Al.sub.2 O.sub.3 :0.92 P.sub.2 O.sub.5 :0.25 SiO.sub.2 : and a formula (anhydrous basis) of:
0.11R(Mg.sub.0.08 Al.sub.0.45 P.sub.0.41 Si.sub.0.06)O.sub.2
(d) The chemical analysis of the MgAPSO-34 of example 63B was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 31.7P.sub.2 O.sub.5 37.0MgO 3.0SiO.sub.2 2.9Carbon 8.3LOI* 21.6______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.24 MgO:1.00 Al.sub.2 O.sub.3 :0.84 P.sub.2 O.sub.5 :0.16 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.07R(Mg.sub.0.06 Al.sub.0.49 P.sub.0.41 Si.sub.0.04)O.sub.2
(e) The chemical analysis for the MgAPSO-34 of example 68B was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 29.8P.sub.2 O.sub.5 40.4MgO 2.3SiO.sub.2 6.9Carbon 10.4LOI* 21.1______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.20 MgO:1.00 Al.sub.2 O.sub.3 :0.97 P.sub.2 O.sub.5 :0.39 SiO.sub.2 : and a formula (anhydrous basis) of:
0.08R(Mg.sub.0.04 Al.sub.0.44 P.sub.0.43 Si.sub.0.09)O.sub.2
(f) The chemical analysis of the MgAPSO-34 of example 74B was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 28.6P.sub.2 O.sub.5 33.9MgO 4.9SiO.sub.2 3.7Carbon 9.0LOI* 27.1______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.43 MgO;1.00 Al.sub.2 O.sub.3 :0.85 P.sub.2 O.sub.5 :0.22 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.08R(Mg.sub.0.10 Al.sub.0.46 P.sub.0.38 Si.sub.0.05)O.sub.2
(g) The chemical analysis for the MgAPSO-35 of example 85B was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 28.3P.sub.2 O.sub.5 42.7MgO 2.8SiO.sub.2 4.0Carbon 9.8LOI* 19.6______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.37 R:0.25 MgO:1.0 Al.sub.2 O.sub.3 :1.08 P.sub.2 O.sub.5 :0.24 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.08(Mg.sub.0.05 Al.sub.0.43 P.sub.0.47 Si.sub.0.05)O.sub.2
(h) The chemical analysis for the MgAPSO-20 of example 101B was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 27.8P.sub.2 O.sub.5 31.4MgO 3.1SiO.sub.2 15.2Carbon 9.7LOI* 21.2______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.74 R:0.28 MgO:1.00 Al.sub.2 O.sub.3 :0.81 P.sub.2 O.sub.5 :0.93 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.15R(Mg.sub.0.06 Al.sub.0.41 P.sub.0.34 Si.sub.0.19)O.sub.2
(i) The chemical analysis for the MgAPSO-43 of example 97B was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 32.3P.sub.2 O.sub.5 33.1MgO 3.6SiO.sub.2 8.2Carbon 9.1LOI* 21.1______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.40R:0.28 MgO:1.00 Al.sub.2 O.sub.3 :0.74 P.sub.2 O.sub.5 :0.43 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.10R(Mg.sub.0.07 Al.sub.0.48 P.sub.0.35 Si.sub.0.10)O.sub.2
(j) The chemical analysis for the MgAPSO-47 of example 104B was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 33.1P.sub.2 O.sub.5 29.3MgO 2.8SiO.sub.2 7.7Carbon 5.7LOI* 25.4______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.24R:0.21 MgO; 1.00 Al.sub.2 O.sub.3 : 0.64 P.sub.2 O.sub.5 : 0.39 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.06R(Mg.sub.0.06 Al.sub.0.51 P.sub.0.33 Si.sub.0.10)O.sub.2
EXAMPLE 108B
EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on clear crystals from the products of examples. Analysis of crystals having a morphology characteristic of the MgAPSO products as prepared in the following referenced examples gave the following analysis based on relative peak heights:
______________________________________(a) MgAPSO-5 (Example 4B): Average of Spot Probes______________________________________Mg 3Al 46P 48Si 3______________________________________(b) MgAPSO-36 (Example 5B): Average of Spot Probes______________________________________Mg 3Al 40P 48Si 9______________________________________(c) MgAPSO-46 (Example 44B): Average of Spot Probes______________________________________Mg 5Al 39P 49Si 6______________________________________(d) MgAPSO-34 (Example 63B): Average of Spot Probes______________________________________Mg 6Al 44P 45Si 6______________________________________(e) MgAPSO-34 (Example 75B): Average of Spot Probes______________________________________Mg 6Al 42P 44Si 8______________________________________(f) MgAPSO-35 (Example 80B): Average of Spot Probes______________________________________Mg 4Al 41P 51Si 4______________________________________(g) MgAPSO-47 (Example 104B): Average of Spot Probes______________________________________Mg 2Al 42P 43Si 13______________________________________
EXAMPLE 109B
Samples of the MgAPSO products were evaluated for adsorption capacities in the as-synthesized form or were calcined in air or nitrogen, to remove at least part of the organic templating agent, as hereinafter set forth. The adsorption capacities of each as-synthesized or calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum at 350.degree. C. prior to measurement. The McBain-Bakr data for the selected MgAPSO products were:
______________________________________(a) Example 4B (MgAPSO-5): Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 99 -183 13.2O.sub.2 3.46 749 -183 15.5Cyclohexane 6.0 57 23.4 7.9neopentane 6.2 100 23.4 5.0H.sub.2 O 2.65 4.6 23.2 16.0H.sub.2 O 2.65 16.8 23.5 21.3______________________________________ *calcined in air at 600.degree. C. for 2.25 hrs.
The above data demonstrate that the pore size of the calcined product is greater than about 6.2 .ANG..
______________________________________(b) Example 101B (MgAPSO-20): Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 99 -183 0.8O.sub.2 3.46 750 -183 2.7H.sub.2 O 2.65 4.6 23.2 16.5H.sub.2 O 2.65 16.8 23.5 19.9______________________________________ *calcined in air at 600.degree. C. for 1.5 hrs.
The above data demonstrate that the pore size of the calcined product is about 3.0 .ANG..
______________________________________(c) Example 63B (MgAPSO-34): Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 100 -183 21.7O.sub.2 3.46 734 -183 33.6isobutane 5.0 300 23 1.3n-hexane 4.3 51 24 10.4H.sub.2 O 2.65 4.6 23 27.1H.sub.2 O 2.65 18.5 24 32.9______________________________________ *calcined in air at 600.degree. C. for 1.5 hours.
The above data demonstrate that the pore size of the calcined product is about 4.3 .ANG..
______________________________________(d) Example 84B (MgAPSO-35): Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 100 -183 6.7O.sub.2 3.46 734 -183 9.2isobutane 5.0 100 24 0.3n-hexane 4.3 51 24 1.1H.sub.2 O 2.65 4.6 23 11.5H.sub.2 O 2.65 19.5 23 17.7______________________________________ *calcined in nitrogen at 500.degree. C. for 2 hrs.
(e) Example 91B (MgAPSO-35): Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 100 -183 11.2O.sub.2 3.46 744 -183 14.0isobutane 5.0 100 22.8 0.2n-hexane 4.3 49 22.3 5.7H.sub.2 O 2.65 4.6 23.1 16.1H.sub.2 O 2.65 17.8 22.9 20.5______________________________________ *calcined at 500.degree. in air for 6.7 hours.
The above data demonstrate that the pore size of the calcined product is about 4.3 .ANG.. In addition, the data demonstrate that in part (d) the template was not sufficiently removed by the calcination.
______________________________________(f) Example 5B (MgAPSO-36): Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 100 -183 12.9O.sub.2 3.46 734 -183 15.4isobutene 5.0 100 24 5.2cyclohexane 6.0 59 23.7 9.0neopentane 6.2 100 24.5 5.5H.sub.2 O 2.65 4.6 23 16.8H.sub.2 O 2.65 20 23.6 23.5______________________________________ *calcined in air at 500.degree. C. for 2.0 hrs. and in air at 600.degree. C. for two additional hours.
The above data demonstrate that the pore size of the calcined product is greater than 6.2 .ANG..
______________________________________(g) Example 44B (MgAPSO-46): Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 100 -183 20.7O.sub.2 3.46 734 -183 24.7neopentane 6.2 100 24.5 8.4isobutene 5.0 100 24 7.8cyclo-hexane 6.0 59 23.7 11.9H.sub.2 O 2.65 4.6 23 22.0H.sub.2 O 2.65 20.0 23.6 27.4______________________________________ *calcined in nitrogen at 500.degree. C. for 1.75 hours.
The above data demonstrate that the pore size of the calcined product is greater than about 6.2 .ANG..
______________________________________(h) Example 104B (MgAPSO-47): Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 99 -183 14.1O.sub.2 3.46 725 -183 29.2isobutane 5.0 100 22.8 0.2n-hexane 4.3 49 23.3 4.2H.sub.2 O 2.65 4.6 23.1 18.5H.sub.2 O 2.65 17.8 22.9 28.7______________________________________ *calcined in air at 500.degree. C. for 1.75 hrs.
The above data demonstrate that the pore size of the calcined product is about 4.3 .ANG..
EXAMPLE 110B
(a) MgAPSO-5, as prepared to in example 4B, was subjected to x-ray analysis. MgAPSO-5 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________7.35 11.71 837.9* 11.19 (sh)12.8 6.92 1114.8 5.99 1815.8* 5.61 116.4* 5.40 219.0* 4.67 (sh)19.65 4.52 48-5221.0 4.23 5422.2 4.004 123.6* 3.770 424.7 3.604 425.75 3.460 3127.2* 3.278 328.9 3.089 2029.8 2.998 1831.8* 2.814 133.5 2.675 534.4 2.607 1736.8 2.442 437.6 2.392 1140.7 2.217 141.3 2.186 342.05 2.149 442.85 2.110 343.4 2.085 244.8 2.023 245.4 1.998 247.4 1.918 651.1 1.787 251.7 1.768 252.4 1.746 155.2 1.664 4______________________________________ *impurity peak
(b) A portion of the as-synthesized MgAPSO-5 of part (a) was calcined in air at 600.degree. C. for about 2.25 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________7.4 11.95 947.9** 11.19 sh8.2** 10.78 sh12.9 6.86 2014.9 5.95 816.4** 5.40 219.3** 4.60 sh19.8 4.48 3321.1 4.21 5222.4 3.969 10024.8 3.590 426.0 3.427 2727.1** 3.290 227.9** 3.198 228.3* 3.154 229.1 3.069 2030.15 2.964 1533.7 2.660 534.6 2.592 1837.0 2.430 437.8 2.380 1041.6 2.171 142.4 2.132 142.9 2.108 143.6 2.076 145.0 2.015 146.2 1.965 147.8 1.903 450.9 1.794 151.6 1.771 155.8 1.648 2______________________________________ *peak may contain impurity **impurity peak
(c) The MgAPSO-5 compositions are generally characterized by the data in Table IX-B below:
TABLE IX-B______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________7.2-7.4 12.28-11.95 m-vs 14.6-14.95 6.07-5.93 w-m19.4-19.8 4.58-4.48 m20.85-21.1 4.26-4.21 vw-vs22.15-22.4 4.01-3.97 m-vs 25.6-25.95 3.480-3.434 m______________________________________
(d) The MgAPSO-5 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table X-B, below:
TABLE X-B______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________7.2-7.4 12.28-11.95 69-10012.65-12.9 7.00-6.86 8-12 14.6-14.95 6.07-5.93 15-3519.4-19.8 4.58-4.48 38-7320.85-21.1 4.26-4.21 (sh)-10022.15-22.4 4.013-3.969 48-100 24.4-24.85 3.648-3.583 0-14 25.6-25.95 3.480-3.434 23-4428.7-29.1 3.110-3.069 12-2029.65-30.15 3.013-2.964 15-21 33.4-33.75 2.683-2.656 2-11 34.2-34.65 2.622-2.589 11-1937.4-37.8 2.405-2.380 5-1140.6-40.7 2.222-2.217 0-141.1-41.6 2.196-2.171 0-341.85-42.4 2.159-2.132 3-4 42.6-43.05 2.122-2.101 0-343.2-43.5 2.094-2.080 0-244.6-45.0 2.032-2.015 0-245.3-45.6 2.002-1.989 0-2 46.1-46.35 1.969-1.959 0-1 47.2-47.75 1.926-1.905 4-650.4 1.811 0-150.9-51.1 1.794-1.787 0-351.6-51.9 1.771-1.762 0-452.2-52.4 1.752-1.746 0-155.2-55.8 1.664-1.648 0-4______________________________________
EXAMPLE 111-B
(a) MgAPSO-11, as prepared to in example 17B, was subjected to x-ray analysis. MgAPSO-11 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________7.3** 12.11 478.0 8.04 199.3 9.51 3012.8** 6.92 (sh)13.1 6.76 1314.75** 6.01 615.6 5.68 2016.1 5.51 318.8 4.72 319.6** 4.53 1520.25 4.39 3221.0* 4.23 10022.0 4.040 (sh)22.3** 3.987 5722.6 3.934 (sh)23.0 3.867 4624.4** 3.648 sh24.6 3.619 925.7** 3.467 1126.3 3.389 2028.5** 3.132 1128.85 3.095 1129.35* 3.043 429.8 2.998 931.4 2.849 632.7 2.739 1334.1 2.629 1034.3** 2.614 sh36.2** 2.481 437.6* 2.392 1239.3 2.293 340.6 2.222 141.9* 2.156 242.9 2.108 444.6 2.032 354.4 1.687 1______________________________________ *Peak may contain impurity **Impurity peak
(b) A portion of the as-synthesized MgAPSO-11 of part (a) was calcined in air at 600.degree. C. for about 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________7.4* 11.95 308.1 10.92 359.6 9.21 3513.0 6.81 1915.8 5.61 3018.2* 4.87 419.7* 4.51 920.15 4.41 2221.2 4.19 10022.3 3.987 7422.9 3.883 sh23.35 3.810 4326.0* 3.427 sh26.3 3.389 1726.7 3.339 sh28.8 3.100 sh29.0* 3.079 1729.5 3.028 930.0* 2.979 431.0* 2.885 331.7 2.823 1532.6 2.747 1533.8 2.652 334.1* 2.629 1536.2 2.481 1237.9 2.374 1543.2 2.094 4______________________________________ *Impurity peak
(c) The MgAPSO-11 compositions are generally characterized by the data of Table XI-B below:
TABLE XI-B______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________9.0-9.6 9.83-9.21 vw-m20.8-21.2 4.27-4.19 vs22.0-22.4 4.04-3.97 vw-m22.4-22.8 3.97-3.90 vw-vs22.8-23.1 3.90-3.85 m______________________________________
(d) The MgAPSO-11 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XII-B, below:
TABLE XII-B______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________ 7.8-8.15 11.33-10.85 sh-359.0-9.6 9.83-9.21 6-6012.9-13.2 6.86-6.71 sh-2215.4-15.9 5.75-5.57 sh-3015.95-16.35 5.56-5.42 sh-318.7-19.1 4.75-4.65 0-420.0-20.5 4.44-4.33 sh-3820.8-21.2 4.27-4.19 10022.0-22.4 4.040-3.969 sh-7222.4-22.8 3.969-3.900 sh-9022.8-23.1 3.900-3.850 21-4823.35 3.810 0-424.4-24.9 3.648-3.576 0-926.2-26.7 3.401-3.339 0-2128.4-28.8 3.143-3.100 sh-1729.3-29.5 3.048-3.028 0-629.6-30.0 3.018-2.979 0-1731.2-31.7 2.867-2.823 0-1532.4-32.8 2.763-2.730 0-1833.8-34.5 2.652-2.600 9-1335.7 2.515 0-336.1-36.8 2.488-2.442 0-1137.5-37.9 2.398-2.374 0-1739.15-39.6 2.301-2.276 0--340.25-40.75 2.241-2.214 0-141.2-41.4 2.191-2.181 0-141.8-42.1 2.161-2.146 0-442.8-43.2 2.113-2.094 0-544.5-44.9 2.036-2.019 0-450.3-50.7 1.814-1.801 0-354.4-54.6 1.687-1.681 0-3______________________________________
EXAMPLE 112B
(a) MgAPSO-16, as prepared to in example 93B, was subjected to x-ray analysis. MgAPSO-16 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________8.6** 10.30 1310.95** 8.10 3611.45 7.73 6413.3** 6.66 2415.85** 5.60 617.25** 5.14 5017.75** 4.99 918.7 4.74 4520.4** 4.35 3520.75** 4.28 1021.1** 4.21 2621.55** 4.12 sh21.85* 4.07 10023.05* 3.858 2626.3** 3.391 526.75* 3.332 2528.45** 3.135 1728.65** 3.116 1829.0* 3.079 1729.9 2.987 2032.0** 2.796 3032.85 2.727 334.6** 2.592 634.85 2.573 435.65** 2.519 1237.9* 2.373 839.95* 2.256 542.0** 2.152 442.9** 2.108 444.3* 2.044 448.55* 1.876 1049.35** 1.846 551.4** 1.778 552.2** 1.752 252.5 1.743 255.0** 1.670 5______________________________________ *Peak may contain impurity **Impurity peak
(b) A portion of the as-synthesized MgAPSO-16 of part (a) was calcined in air at 600.degree. C. for about 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.THETA. d, (.ANG.) 100 I/Io______________________________________8.7** 10.16 2511.0** 8.04 18511.4 7.76 sh13.6** 6.51 20017.5** 5.07 5018.7 4.75 1021.2** 4.23 4522.2* 4.004 10022.8* 3.900 1523.7** 3.754 3025.1** 3.548 1526.4** 3.376 1527.3* 3.267 4028.7** 3.110 6529.0* 3.079 sh29.7 3.008 4532.0** 2.797 1532.6** 2.747 5033.2 2.706 sh34.6* 2.592 1035.6** 2.522 5______________________________________ *Peak may contain impurity **Impurity peak
(c) The MgAPSO-16 compositions are characterized by the data of Table XIII-B below:
TABLE XIII-B______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________11.4-11.5 7.76-7.69 m18.7-18.8 4.75-4.72 w-m21.85-22.2 4.07-4.00 vs22.8-23.3 3.900-3.818 w-m26.75-27.3 3.332-3.267 w-m29.7-29.9 3.008-2.988 w-m______________________________________
(d) The MgAPSO-16 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XIV-B, below:
TABLE XIV-B______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________11.5-11.5 7.76-7.69 sh-6418.7-18.8 4.75-4.72 10-4521.85-22.2 4.07-4.00 10022.8-23.3 3.900-3.818 15-2626.75-27.3 3.332-3.267 16-4028.95-29.0 3.084-3.079 sh-1729.7-29.9 3.008-2.988 9-4532.8-33.2 2.730-2.968 sh-3 34.6-34.85 2.592-2.573 4-1037.8-38.0 2.380-2.368 4-7 39.4-39.95 2.287-2.256 2-544.3-44.5 2.044-2.036 2-1048.55-48.6 1.876-1.873 7-1052.4-52.5 1.746-1.743 1-2______________________________________
EXAMPLE 113B
(a) MgAPSO-20, as prepared in example 98B, was subjected to x-ray analysis. MgAPSO-20 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________13.9 6.36 4419.75 4.50 4222.05 4.029 324.2 3.676 10028.0 3.184 1231.4 2.849 1034.5 2.601 1437.35 2.408 138.45* 2.340 140.0 2.253 442.55 2.124 547.3 1.921 449.0* 1.859 149.4* 1.846 251.7 1.768 8______________________________________ *impurity peak
(b) A portion of the as-synthesized MgAPSO-20 of part (a) was calcined in air at 600.degree. C. for about 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern of below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________14.15 7.27 10020.05 4.43 2022.45 3.964 424.6 3.616 5428.5 3.132 1532.0 2.799 1035.0 2.564 10______________________________________
(c) The MgAPSO-20 compositions are characterized by the data of Table XV-B below:
TABLE XV-B______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________13.8-14.2 6.42-6.23 m-vs 19.6-20.15 6.53-4.41 m24.1-24.7 3.695-3.603 m-vs27.9-28.6 3.198-3.121 w 31.3-32.05 2.861-2.791 w34.35-35.0 2.610-2.601 w______________________________________
(d) The MgAPSO-20 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XVI-B, below:
TABLE XVI-B______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________13.8-14.2 6.42-6.23 42-100 19.6-20.15 4.55-4.41 22-4321.95-22.45 4.050-3.964 3-724.1-24.7 3.695-3.603 56-10027.9-28.6 3.198-3.121 11-15 31.3-32.05 2.861-2.791 10-1234.35-35.0 2.610-2.601 10-16 37.2-37.35 2.417-2.408 1-239.9-40.0 2.260-2.253 3-4 42.4-42.55 2.130-2.124 547.15-47.3 1.927-1.921 4-551.55-51.7 1.772-1.768 8______________________________________
EXAMPLE 114B
(a) MgAPSO-34, as prepared in example 68B, was subjected to x-ray analysis. MgAPSO-34 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________9.5 9.32 10012.8 6.91 1514.1 6.30 1517.95 4.94 2120.5 4.32 9222.2 4.002 423.0 3.864 525.15 3.540 2325.8 3.455 1827.5 3.243 328.3 3.151 429.5 3.029 430.5 2.932 3331.2 2.866 2231.6* 2.833 532.25 2.775 334.35 2.611 738.6 2.332 236.2 2.480 839.6 2.277 443.1 2.100 347.5 1.915 4______________________________________48.9 1.862 650.9 6.795 453.0 1.727 454.5 1.684 255.75 1.649 4______________________________________
(b) A portion of the as-synthesized MgAPSO-34 of part (a) was calcined in air at 550.degree. C. for about 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________9.7 9.12 10013.1 6.76 2214.2 6.24 116.3 5.44 1518.1 4.90 1019.3 4.60 320.95 4.24 3121.6* 4.11 sh22.4 3.969 323.35 3.809 325.35 3.513 1126.3 3.389 1028.5 3.132 430.0 2.979 sh31.0 2.885 2333.8 2.652 235.0 2.564 336.6 2.455 143.7 2.071 149.4 1.845 251.3 1.781 252.2 1.752 153.1 1.725 154.0 1.698 2______________________________________ *impurity peak
(c) The MgAPSO-34 compositions are characterized by the data of Table XVII-B below:
TABLE XVII-B______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________9.3-9.7 9.51-9.12 vs15.8-16.3 5.61-5.44 w-m20.25-21.0 4.39-4.23 m-vs25.7-26.3 3.466-3.389 vw-m30.0-30.8 2.979-2.903 vw-m30.9-31.4 2.894-2.849 w-m______________________________________
(d) The MgAPSO-34 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XVIII-B below.
TABLE XVIII-B______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________9.3-9.7 9.51-9.12 99-10012.6-13.1 7.03-6.76 11-2513.8-14.3 6.42-6.19 0-2415.8-16.3 5.61-5.44 13-5617.8-18.2 4.98-4.87 5-2819.1-19.4 4.65-4.58 0-320.25-21.0 4.39-4.23 22-10022.2-22.5 4.004-3.952 0-622.8-23.4 3.900-3.802 0-624.9-25.4 3.576-3.507 6-2725.7-26.3 3.466-3.389 6-2927.4-28.0 3.255-3.187 0-428.2-28.8 3.164-3.100 0-429.0-29.6 3.079-3.018 0-630.0-30.8 2.979-2.903 0-3430.9-31.4 2.894-2.849 16-3032.2-32.4 2.780-2.763 0-433.8-34.5 2.401-2.600 0-1534.6-35.0 2.592-2.564 0-436.0-36.6 2.495-2.456 0-438.4-39.0 2.344-2.309 0-243.0-43.7 2.103-2.071 0-344.6-45.0 2.032-2.015 0-147.2-47.6 1.926-1.910 0-448.3-49.4 1.884-1.845 0-650.2 1.817 0-250.7-51.4 1.801-1.778 0-451.3-51.5 1.781.1.774 0-252.9-53.1 1.731.1.725 0-454.1-54.6 1.695-1.681 0-455.5-55.9 1.656-1.645 0-4______________________________________
EXAMPLE 115B
(a) MgAPSO-35, as prepared in example 85B, was subjected to x-ray analysis. MgAPSO-35 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 8.6 10.28 1110.9 8.12 44 11.4** 7.76 213.4 6.61 2015.9 5.57 917.3 5.13 8017.7 5.01 sh 18.7** 4.75 120.9 4.25 54 21.9* 4.06 100 22.7** 3.917 sh 23.25 3.826 2724.9 3.576 625.8 3.453 1 26.85* 3.320 1627.1 3.290 sh28.3 3.153 4429.0 3.079 10 31.45* 2.844 sh32.1 2.788 37 32.4* 2.763 sh 34.3* 2.614 7 35.2** 2.550 135.8 2.508 2 37.6* 2.392 239.4 2.287 140.9 2.206 141.8 2.161 442.5 2.127 5 44.5* 2.036 447.5 1.914 2 48.3* 1.884 448.8 1.866 449.4 1.845 551.0 1.791 755.2 1.664 4______________________________________ *peak may contain impurity **impurity
(b) A portion of the as-synthesized MgAPSO-35 of part (a) was calcined in air at 500.degree. C. for about 68 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 8.5 10.40 2110.8 8.19 100 11.3* 7.83 sh13.3 6.66 7615.8 5.61 317.2 5.16 31 20.15* 4.41 11020.8 4.27 sh 21.25* 4.18 97 21.85 4.07 40 22.8* 3.900 4323.1 3.850 sh 24.2* 3.678 624.8 3.590 6 26.2* 3.401 4527.0 3.302 1027.3 3.267 1028.3 3.153 2429.5 3.028 19 30.9* 2.894 531.4 2.849 732.2 2.780 1932.7 2.739 sh 33.8* 2.652 434.4 2.607 5 35.3* 2.543 2136.0 2.495 4 37.2* 2.417 438.4 2.344 639.8 2.265 440.9 2.206 241.9 2.156 542.6 2.122 6 43.5* 2.085 344.8 2.023 245.1 2.010 448.4 1.881 249.3 1.848 251.3 1.781 355.5 1.656 5______________________________________ *impurity peak
(c) The MgAPSO-35 compositions are generally characterized by the data of Table XIXB below:
TABLE XIXB______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________10.6-11.1 8.35-7.97 m-vs13.1-13.7 6.76-6.46 w-vs17.0-17.6 5.22-5.04 m-s.sup.20.6-21.2 4.31-4.19 vw-m21.6-22.2 4.11-4.00 m-vs28.1-28.8 3.175-3.100 m______________________________________
(d) The MgAPSO-35 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XX-B, below:
TABLE XX-B______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.3-8.8 10.65-10.05 10-2110.6-11.1 8.35-7.97 36-10013.1-13.7 6.76-6.46 17-10015.7-16.0 5.64-5.54 0-917.0-17.6 5.22-5.04 25-8017.7-17.8 5.01-4.98 0-sh20.6-21.2 4.31-4.19 sh-5421.6-22.2 4.11-4.00 40-10023.0-23.7 3.867-3.754 sh-2724.6-25.2 3.619-3.534 5-825.8-26.4 3.453-3.376 0-826.6-27.3 3.351-3.267 10-1627.1 3.290 sh-1028.1-28.8 3.175-3.100 24-4428.9-29.7 3.089-3.008 5-2331.45-31.5 2.844-2.840 sh-731.9-32.4 2.805-2.763 19-3732.4-32.7 2.763-2.739 sh34.1-34.7 2.629-2.585 5-935.6-36.1 2.522-2.488 0-437.1-38.0 2.404-2.368 0-639.4-39.9 2.287-2.259 0-440.8-40.9 2.212-2.206 0-141.7-42.2 2.166-2.141 0-542.2-42.7 2.132-2.118 0-644.5-44.8 2.036-2.023 0-745.0-45.1 2.014-2.010 0-147.4-47.7 1.914-1.907 0-248.2-48.6 1.888-1.873 0-448.7-49.0 1.870- 1.859 0-449.3-49.7 1.848-1.834 0-550.8-51.5 1.797-1.774 0-755.2-55.6 1.664-1.653 0-4______________________________________
EXAMPLE 116B
(a) MgAPSO-36, as prepared in example 5B, was subjected to x-ray analysis. MgAPSO-36 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 7.4** 11.95 sh 7.9 11.19 100 8.1 10.92 sh 12.8** 6.92 3 13.45 6.58 6 14.75** 6.01 415.7 5.64 (sh)16.3 5.44 3118.9 4.70 41 19.5** 4.55 7 20.7* 4.29 49 21.55 4.12 (sh)21.8 4.077 (sh) 22.35* 3.978 4222.8 3.900 (sh)23.8 3.739 9 25.7** 3.466 627.1 3.290 1428.2 3.164 10 28.9* 3.089 1230.1 2.969 731.8 2.814 11 33.0* 2.714 3 34.6* 2.592 1635.7 2.515 4 37.6* 2.349 339.3 2.293 140.1 2.249 341.3 2.186 4 42.0** 2.151 243.0 2.103 244.0 2.058 245.3 2.002 146.6 1.949 147.3 1.922 348.8 1.867 151.1 1.787 253.7 1.707 255.4 1.659 3______________________________________ *peak may contain impurity **impurity peak
(b) A portion of the as-synthesized MgAPSO-36 of part (a) was calcined in air at 500.degree. C. for about 2 hours and at 600.degree. C. for an additional 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________7.4** 11.95 sh7.9 11.19 1008.2 10.78 sh12.8** 6.92 313.45 6.58 814.9** 5.95 215.9 5.57 sh16.5 5.37 2419.3 4.60 3819.75** 4.50 sh20.8 4.27 2521.2** 4.19 sh21.8 4.08 sh22.35 3.978 2522.6** 3.934 sh23.0 3.867 sh23.9 3.723 524.9** 3.576 125.8** 3.453 427.2 3.278 1628.35 3.148 729.1* 3.69 1029.9 2.988 330.4* 2.940 532.0 2.797 833.2 2.698 135.0* 2.564 736.0 2.495 337.7* 2.386 239.5 2.281 140.3 2.238 241.3 2.186 442.0** 2.151 243.5 2.080 144.3 2.045 145.4 1.998 147.6 1.910 351.2 1.784 155.5 1.656 1______________________________________ *peak may contain impurity **impurity peak
(c) The MgAPSO-36 compositions are generally characterized by the data of Table XXI-B below:
TABLE XXI-B______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________7.8-8.0 11.33-11.05 vs16.3-16.5 5.44-5.37 m18.9-19.3 4.70-4.60 m20.7-20.8 4.29-4.27 m22.35 3.98 m______________________________________
(d) The MgAPSO-36 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXII-B below:
TABLE XXII-B______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________7.8-8.0 11.33-11.05 1008.1-8.2 10.92-10.78 0-sh 13.45 6.58 6-815.7-15.9 5.64-5.57 sh16.3-16.5 5.44-5.37 24-3118.9-19.3 4.70-4.60 38-4120.7-20.8 4.29-4.27 25-4921.0 4.23 0-sh21.55-21.8 4.12-4.08 sh21.8-21.9 4.077-4.058 sh22.35 3.978 25-4222.8-23.0 3.900-3.867 (sh)23.8-23.9 3.739-3.723 5-927.1-27.2 3.290-3.278 14-16 28.1-28.35 3.176-3.148 7-1028.8-29.1 3.100-3.069 10-1229.9-30.1 2.988-2.969 3-731.8-32.0 2.814-2.797 8-1133.0-33.2 2.714-2.698 1-334.6-35.0 2.592-2.564 7-1635.7-36.0 2.515-2.495 3-437.6-37.7 2.392-2.386 2-339.3-39.5 2.293-2.281 140.1-40.3 2.249-2.238 2-341.3 2.186 443.0-43.5 2.103-2.080 1-243.95-44.3 2.060-2.045 1-245.2-45.4 2.006-1.998 146.6 1.949 0-147.3-47.6 1.922-1.910 348.8 1.867 0-151.1-51.2 1.787-1.784 1-253.7 1.707 0-255.3-55.5 1.661-1.656 1-3______________________________________
EXAMPLE 117B
(a) MgAPSO-39, as prepared in example 55B, was subjected to x-ray analysis. MgAPSO-39 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 8.1** 10.92 6 8.5** 10.40 15 8.9** 9.98 1 9.45* 9.34 3012.4** 7.13 213.4* 6.60 4814.2** 6.22 214.4** 6.15 214.6** 6.06 215.65** 5.66 418.15 4.89 3320.3** 4.38 1721.3* 4.18 7022.1** 4.027 1322.6* 3.929 10023.15** 3.844 1026.4** 3.375 327.0 3.301 427.8** 3.208 328.0* 3.191 428.7* 3.113 929.7 3.007 1330.3 2.953 2531.7** 2.823 532.7 2.736 1234.1* 2.632 735.1** 2.555 236.7* 2.448 238.1* 2.361 939.25** 2.295 241.0 2.200 243.3 2.089 243.8 2.067 145.0 2.015 146.2* 1.966 247.2* 1.926 148.8 1.867 449.4 1.845 351.45* 1.776 452.3 1.749 254.55 1.683 2______________________________________ *peak may contain impurity **impurity peak
(b) The MgAPSO-39 compositions are generally characterized by the data of Table XXIII-B below:
TABLE XXIII-B______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________9.2-9.6 9.61-9.21 m13.1-13.5 6.76-6.56 m17.8-18.3 4.98-4.85 m20.8-21.3 4.27-4.17 m-vs22.2-22.8 4.00-3.90 vs30.0-30.3 2.979-2.950 w-m______________________________________
(c) The MgAPSO-39 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXIV-B below.
TABLE XXIV-B______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________9.2-9.6 9.61-9.21 20-5313.1-13.5 6.76-6.56 25-5317.8-18.3 4.98-4.85 23-3420.8-21.3 4.27-4.17 79-10022.2-22.8 4.002-3.900 97-100 26.8-27.05 3.326-3.296 3-428.0-28.2 3.191-3.175 0-428.6-28.8 3.121-3.100 sh-1729.4-29.8 3.038-2.998 13-2030.0-30.3 2.979-2.950 17-2932.4-32.8 2.763-2.730 10-1633.9-34.2 2.644-2.622 sh-11 36.7-36.85 2.448-2.439 0-237.8-38.1 2.380-2.362 5-940.7-41.0 2.217-2.201 0-543.0-43.4 2.103-2.085 0-245.0 2.014 0-146.2-46.3 1.966-1.961 0-247.2-47.3 1.926-1.922 0-1 48.5-48.85 1.877-1.864 4-549.0-49.5 1.859-1.841 0-351.0-51.5 1.791-1.778 3-552.1-52.4 1.755-1.746 0-454.2-54.6 1.692-1.681 0-2______________________________________
EXAMPLE 118B
(a) MgAPSO-43, as prepared in example 92B, was subjected to x-ray analysis. MgAPSO-43 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________6.5* 13.63 87.6** 11.66 3523.3 7.20 10013.05** 6.77 414.45** 6.14 415.15* 5.85 216.5** 5.37 317.3 5.13 1219.7* 4.51 320.35** 4.37 221.45* 4.14 4922.65** 3.928 634.9** 3.726 324.0 3.701 324.35 3.653 226.7* 3.336 727.6 3.232 3928.05* 3.182 1828.55* 3.126 529.65** 2.013 130.95** 2.889 232.8** 2.729 733.05 2.710 835.8* 2.510 338.3** 2.350 239.55** 2.278 143.75** 2.070 244.05** 2.055 145.4 1.997 345.65** 1.998 349.0** 1.859 351.1* 1.788 452.0* 1.759 153.0 1.728 353.7 1.707 2______________________________________ *peak may contain impurity **impurity peak
(b) A portion of the as-synthesized MgAPSO-43 of part (a) was calcined in air at 500.degree. C. for about 1 hour and at 600.degree. C. for about 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________ 6.95* 12.73 30 8.15* 10.87 4712.95 6.83 3517.4 5.10 1017.4 5.10 1021.45 4.14 10023.2* 3.832 4428.15 3.167 25______________________________________ *impurity peak
(c) The MgAPSO-43 compositions are generally characterized by the data of Table XXV-B below:
TABLE XXV-B______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________12.3-12.95 7.20-6.83 m-vs17.3-17.45 5.13-5.09 w21.45-21.6 4.15-4.12 m-vs27.6-27.75 3.232-3.215 m33.05-33.2 2.710-2.699 w______________________________________
(d) The MgAPSO-43 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXVI-B below:
TABLE XXVI-B______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________12.3-12.95 7.20-6.83 35-10015.15-15.5 5.85-5.37 2-417.3-17.45 5.13-5.09 1219.7-19.85 4.51-4.47 3-521.45-21.6 4.15-4.12 49-10024.35-24.5 3.653-3.635 226.7-26.85 3.336-3.319 7-927.6-27.75 3.232-3.215 39-5028.05-28.2 3.182-3.165 18-2528.55-28.75 3.126-3.107 5-633.05-33.2 2.710-2.699 8-1235.8-35.9 2.510-2.502 3-445.4-45.55 1.997-1.991 351.1-51.2 1.788-1.785 452.0-52.25 1.759-1.750 1-253.0-53.1 1.728-1.725 3-453.7-53.95 1.707-1.700 2______________________________________
EXAMPLE 119B
(a) MgAPSO-44, as prepared in example 88B, was subjected to X-ray analysis. MgAPSO-44 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________ 6.7** 13.19 64 7.3** 12.11 12 9.35 9.46 100 12.95* 6.84 1613.7 6.46 24.5 6.11 5 14.8** 5.99 316.1 5.54 3517.3 5.13 718.9 4.70 8 19.6** 4.53 920.7 4.29 100 20.9** 4.25 sh21.7 4.10 13 22.3** 3.986 2822.5 3.952 sh23.0 3.867 724.3 3.663 37 25.8** 3.453 sh26.1 3.414 727.5 3.243 10 28.8** 3.998 429.6 3.018 sh 29.9* 2.988 1530.7 2.912 4831.4 2.849 132.4 2.763 432.7 2.739 3 33.4** 2.683 1 34.3** 2.614 334.8 2.578 435.4 2.536 636.8 2.442 1 37.5** 2.398 338.4 2.344 139.1 2.304 139.8 2.265 1 42.0* 2.146 643.4 2.085 246.5 1.957 147.1 1.929 3 48.0* 1.895 848.5 1.877 550.1 1.821 1051.8 1.768 153.6 1.710 1054.6 1.6871 155.3** 1.661 1______________________________________ *peak may contain impurity **impurity peak
(b) A portion of the as-synthesized MgAPSO-44 of part (a) was calcined in air for 2.5 hours at 500.degree. C. and then for 0.25 hour at 600.degree. C. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________ 2.9** 30.46 8 7.35** 12.03 64 8.9** 9.94 sh 9.1** 9.72 sh 9.5 9.31 100 12.8* 6.92 3513.9 6.37 4 14.7** 6.07 316.0 5.54 2017.8 4.98 53 19.6** 4.53 1420.6 4.31 82 21.1** 4.21 16 22.3* 3.986 sh-2823.0 3.867 7-8 25.0* 3.562 18 25.8* 3.453 1727.6 3.232 128.2 3.164 3 28.9** 3.089 429.8 2.998 4 30.5* 2.931 2431.0 2.885 1631.6 2.831 sh32.2 2.780 133.2 2.698 sh 33.5** 2.675 3 34.3** 2.614 834.8 2.578 136.0 2.494 3 37.7** 2.386 238.5 2.338 139.0 2.309 139.6 2.276 3 42.0* 2.151 1 4.9** 2.108 243.3 2.090 1 47.5* 1.918 448.8 1.866 350.8 1.797 451.6 1.771 153.0 1.728 4 54.3** 1.689 155.6 1.656 1______________________________________ *peak may contain impurity **impurity peak
(c) The MgAPSO-44 compositions are generally characterized by the data of Table XXVII-B below:
TABLE XXVII-B______________________________________2.THETA. d, (.ANG.) 100 .times.I/Io______________________________________ 9.2-9.45 9.61-9.37 vs15.9-16.1 5.57-5.50 m17.2-18.0 5.16-4.93 vw-m 20.5-20.75 4.33-4.28 m-vs24.3-25.0 3.663-3.562 w-m30.5-31.0 2.931-2.885 w-m______________________________________
(d) the MgAPSO-44 compositions for which x-ray powder diffraction data have been obtained to date have pattens which are characterized by the x-ray powder diffraction shown in Table XXVIII-B below:
TABLE XXVIII-B______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________ 9.2-9.45 9.61-9.37 100 12.8-13.0* 6.92-6.81 11-3513.6-14.0 6.51-6.33 2-414.5-14.6 6.11-6.07 0-515.9-16.1 5.57-5.50 20-3617.2-18.0 5.16-4.93 718.8-19.0 4.72-4.67 7-53 20.5-20.75 4.33-4.28 58-10021.7-21.8 4.10-4.08 0-1822.3-22.6 3.986-3.924 sh23.0-23.3 3.867-3.817 8 24.3-25.0* 3.663-3.562 17-58 25.8-26.15* 3.453-3.406 10-1827.5-27.8 3.243-3.209 1-1228.2 3.175 0-329.6-29.8 3.018-2.998 0-sh 29.7-30.5* 3.008-2.931 4-1530.5-31.0 2.931-2.885 16-4831.4-31.6 2.849-2.831 sh-132.2-32.5 2.780-2.755 1-532.7-33.2 2.739-2.698 sh-334.8 3.578 0-135.3-36.0 2.543-2.495 3-636.8 2.442 0-138.4-39.1 2.344-2.338 0-139.0-39.1 2.309-2.304 0-139.6-40.0 2.276-2.254 0-1 42.0-42.2* 2.151-2.141 0-643.3-43.6 2.090-2.076 0-246.5 1.953 0-147.1- 47.5 1.929-1.914 0-5 48.0-48.2* 1.895-1.888 0-848.5-48.8 1.877-1.866 0-550.0-50.8 1.824-1.797 4-1051.6-51.8 1.771-1.765 0-153.0-53.8 1.728-1.704 4-1054.3-54.6 1.689-1.681 0-2______________________________________ *peak may contain impurity
EXAMPLE 120B
(a) MgAPSO-46, as prepared in example 44B, was subjected to x-ray analysis. MgAPSO-46 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________6.6 13.44 37.7 11.48 10010.1 8.76 <112.4 7.15 213.2 6.71 213.75 6.44 314.9 5.95 115.3 5.79 216.6 5.33 317.4 5.10 <119.8 4.48 120.45 4.34 420.7 4.29 sh21.5 4.13 1222.75 3.906 624.2 3.682 325.2 3.534 <126.85 3.320 427.7 3.219 328.2 2.163 228.7 3.109 429.8 3.000 131.1 2.873 231.7 2.823 <132.9 2.722 <134.2 2.622 135.85 2.505 236.5 2.462 <137.2 2.417 <138.4 2.344 <139.6 2.276 <141.0 2.201 <142.2 2.141 <143.9 2.062 145.9 1.977 <147.5 1.914 <149.4 1.845 <150.1 1.821 <151.4 1.778 <152.2 1.752 <1______________________________________
(b) A portion of the as-synthesized MgAPSO-46 of part (a) was calcined in nitrogen at 500.degree. for about 1.75 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________6.8 13.0 87.8 11.33 10013.5 6.56 814.0 6.33 315.2 5.83 915.6 5.68 sh16.95 5.23 1120.2 4.40 sh20.7 4.29 621.7 4.10 1023.0 3.867 624.4 3.648 327.2 3.278 427.9 3.198 328.4 3.143 sh28.9 3.089 630.2 2.959 231.4 2.849 332.0 2.797 133.4 2.683 234.2 2.622 236.2 2.481 237.0 2.430 <140.2 2.243 <141.3 2.186 144.2 2.049 146.3 1.961 <147.9 1.899 <150.5 1.807 151.9 1.762 <152.6 1.740 <1______________________________________
(c) The MgAPSO-46 compositions are generally characterized by the data of Table XXIX-B below:
TABLE XXIX-B______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________7.2-8.1 12.28-10.92 vs21.2-21.8 4.19-4.08 w-m22.5-23.0 3.952-3.867 vw-m26.6-27.2 3.351-3.278 vw-w28.5-29.0 3.132-3.079 vw-w______________________________________
(d) The MgAPSO-46 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXX-B below:
TABLE XXX-B______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________6.5-6.9 13.60-12.81 3-107.2-8.1 12.28-10.92 100 9.8-10.3 9.03-8.59 0-112.4 7.14 0-412.9-13.5 6.86-6.56 2-813.5-14.0 6.56-6.33 3-814.8-15.2 5.99-5.83 1-915.2-15.8 5.83-5.61 (sh)-516.5-17.6 5.37-5.04 3-1117.3-17.4 5.13-5.10 0-119.7-20.2 4.51-4.40 (sh)-520.3-20.7 4.37-4.29 4-921.2-21.8 4.19-4.08 10-3622.5-23.0 3.952-3.867 6-2023.7-24.4 3.754-3.648 3-1125.0-25.5 3.562-3.648 0-126.6-27.2 3.351-3.278 4-1727.5-27.9 3.243-3.198 3-1228.0-28.4 3.255-3.143 sh-228.5-29.0 3.132-3.079 4-1529.6-30.2 3.018-2.959 1-430.9-31.4 2.894-2.849 2-631.6-32.0 2.831-2.797 1-332.6-33.4 2.747-2.683 1-233.95-34.4 2.640-2.607 1-435.7-36.2 2.515-2.481 2-636.3-37.0 2.475-2.430 0-237.0-37.6 2.430-2.392 0-137.9-38.4 2.374-2.344 0-139.5- 40.2 2.281-2.243 0-140.7-41.3 2.217-2.186 0-143.7-44.3 2.071-2.45 0-145.8-46.4 1.981-1.957 0-147.3-47.9 1.922-1.899 0-149.2-49.3 1.852-1.848 0-149.9-50.5 1.828-1.807 0-151.2-51.9 1.784-1.762 0-152.1-52.6 1.755-1.740 0-1______________________________________
EXAMPLE 121-B
(a) MgAPSO-47, as prepared in example 104B, was subjected to x-ray analysis. MgAPSO-47 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________ 9.5 9.29 100 12.95 6.84 913.9 6.36 5 16.05 5.52 22 17.65 5.03 9 19.05 4.66 2 20.65 4.30 5321.9 4.06 7 22.45* 3.961 2 23.05 3.859 7 24.75 3.598 21 25.95 3.432 1227.7 3.222 5 27.95 3.190 3 28.55* 3.126 1 29.55 3.022 330.6 2.919 2130.9 2.893 sh31.5 2.837 232.4 2.763 1 33.25 2.695 2 34.55 2.597 4 34.95 2.567 135.8 2.510 338.5 2.338 239.1 2.305 139.7 2.270 242.5 2.126 243.4 1.085 147.7 1.907 248.7 1.870 450.4 1.810 351.7 1.768 1 52.45 1.745 153.3 1.719 254.1 1.695 154.6 1.681 155.9 1.645 2______________________________________ *Impurity peak
(b) A portion of the as-synthesized MgAPSO-47 of part (a) was calcined in air at 500.degree. C. for about 1.75 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________ 9.65 9.17 100 13.05 6.79 2014.2 6.25 416.2 5.46 1418.0 4.92 1119.3 4.60 3 20.85 4.26 3322.3 3.980 2 22.6* 3.933 323.3 3.819 4 23.6* 3.771 1 24.55* 3.626 2 25.25 3.556 1226.2 3.400 1028.0 3.188 228.5 3.132 4 29.95 2.983 2 30.95 2.889 1531.4 2.849 sh34.8 2.575 336.5 2.459 2______________________________________ *Impurity peak
(c) The MgAPSO-47 compositions are generally characterized by the date of Table XXXI-B below:
TABLE XXXI-B______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________9.5-9.65 9.33-9.17 vs 12.85-13.05 6.89-6.79 vw-m16.0-16.2 5.54-5.46 w-m 20.6-20.85 4.32-4.26 m-s24.75-25.3 3.598-3.526 vw-m30.55-30.95 2.925-2.889 w-m______________________________________
(d) the MgAPSO-47 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXXII-B below:
TABLE XXXII-B______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________ 9.5-9.65 9.33-9.17 10012.85-13.05 6.89-6.79 7-2013.9-14.2 6.36-6.25 3-716.0-16.2 5.54-5.46 14-4117.65-18.0 5.03-4.92 4-1119.0-19.3 4.67-4.60 2-3 20.6-20.85 4.32-4.26 33-8921.9-22.3 4.06-3.98 2-723.0-23.3 3.866-3.819 3-1124.75-25.3 3.598-3.526 8-2225.85-26.2 3.444-3.400 7-1827.6-28.0 3.229-3.188 2-727.95-28.5 3.190-3.132 1-4 29.5-29.95 3.030-3.983 2-530.55-30.95 2.925-2.889 13-3630.9-31.4 2.891-2.849 sh31.4-31.5 2.849-2.837 0-332.4 2.763 0-1 33.25 2.695 0-334.4-34.8 2.606-2.575 3-734.95 2.567 0-1 35.8-36.55 2.510-2.459 1-438.5 2.338 0-2 39.1-39.65 2.305-2.273 0-439.6-39.7 2.275-2.270 0-442.5-42.8 2.126-2.115 0-343.3-43.8 2.091-2.067 0-247.6-47.7 1.911-1.907 0-348.7-49.3 1.870-1.848 1-750.4-51.1 1.810-1.787 1-551.7 1.768 0-1 52.45 1.745 0-153.3 1.719 0-254.1 1.695 0-154.7 1.681 0-155.9 1.645 0-2______________________________________
EXAMPLE 122B
In order to demonstrate the catalytic activity of the MgAPSO compositions, calcined samples of MgAPSO products were tested for catalytic cracking of n-butane using a bench-scale apparatus.
The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm. I.D. In each test the reactor was loaded with particles of the test MgAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The MgAPSO samples had been previously calcined in air or nitrogen to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500.degree. C. for one hour. The feedstock was a helium-n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.
The pseudo-first-order rate constant (k.sub.A) was calculated to determine the relative catalytic activity of the MgAPSO compositions. The k.sub.A value (cm.sup.3 /g min) obtained for the MgAPSO compositions are set forth, below, in Table XXX-B:
TABLE XXX-B______________________________________ Prepared inMgAPSO Example No. Rate Constant (k.sub..ANG.)*______________________________________MgAPSO-35 80B 2.6MgAPSO-34 63B 4.1MgAPSO-35 82B 0.9MgAPSO-36 5B 18.0MgAPSO-46 44B 7.3MgAPSO-47 104B 1.7______________________________________ *Prior to activation of the MgAPSO samples of the following examples such were calcined as follows: (a) Example 80B: calcined in air at 600.degree. for 2.25 hours; (b) Example 63B: calcined in air at 550.degree. C. for 2 hours; (c) Example 82B: calcined in nitrogen at 425.degree. C. for 2 hours; (d) Example 5B: calcined in air at 500.degree. C. for 2 hours and then at 600.degree. C. for 2 hours; (e) Example 44B: calcined in nitrogen at 500.degree. C. for 1.75 hours; and (f) Example 104B: calcined in air at 500.degree. C. for 1.75 hours.
IRON-ALUMINUM-PHOSPHORUS-SILICON-OXIDE SIEVES
Molecular sieves containing iron, aluminum phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
PREPARATIVE REAGENTS
In the following examples the FeAPSO compositions were prepared using numerous reagents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:
(a) Alipro: aluminum isopropoxide, Al(OCH(CH.sub.3).sub.2).sub.3 ;
(b) LUDOX-LS: LUDOX-LS is the trademark of Du Pont for an aqueous solution of 30 weight percent SiO.sub.2 and 0.1 weight percent Na.sub.2 O;
(c) CATAPAL: trademark for hydrated aluminum oxide containing about 75 wt. % Al.sub.2 O.sub.3 (pseudo-boehmite phase) and about 25 wt. percent water.
(c) Fe(Ac).sub.2 : Iron (II) acetate;
(d) FeSO.sub.4 : Iron (II) sulfate hexahydrate;
(e) H.sub.3 PO.sub.4 : 85 weight percent phosphoric acid in water;
(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(h) Pr.sub.2 NH: di-n-propylamine ((C.sub.3 H.sub.7).sub.2 NH);
(i) Pr.sub.3 N: tri-n-propylamine ((C.sub.3 H.sub.7).sub.3 N);
(j) Quin: Quinuclidine (C.sub.7 H.sub.13 N);
(k) MQuin: Methyl Quinuclidine hydroxide (C.sub.7 H.sub.13 NCH.sub.3 OH);
(l) TMAOH: tetramethylammonium hydroxide pentahydrate; and
(m) C-hex: cyclohexylamine.
EXAMPLES 1C to 16C
(a) Examples 1C to 8C were carried out to demonstrate the preparation of FeAPSO-34 and FeAPSO-5. The reaction mixtures were prepared by grinding the aluminum isopropoxide in a blender followed by slowly adding the H.sub.3 PO.sub.4 solution with mixing. A solution/dispersion of iron acetate in water was added and then the LUDOX-LS was added. The organic templating agent was then added to this mixture, or in some cases one-half of this mixture, and the mixture blended to form a homogeneous mixture. The number of moles of each component in the reaction mixture was as follows:
______________________________________ Component Moles______________________________________ Al.sub.2 O.sub.3 0.9 P.sub.2 O.sub.5 0.9 SiO.sub.2 0.2** FeO* 0.2 TEAOH 1.0 H.sub.2 O 50______________________________________ *Iron (II) acetate reported as Iron (II) oxide. **SiO.sub.2 was 0.6 in examples 5C to 8C
Each reaction mixture was sealed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated in an oven at a temperature (see Table I-C), time (see Table I-C) and at the autogeneous pressure. The solid reaction product was recovered by filtration, washed with water and dried at room temperature. The products were analyzed and the observed FeAPSO products reported in Table I-C.
(b) Examples 9C to 16C were carried out to demonstrate the preparation of FeAPSO-11 and FeAPSO-5. The reaction mixtures were prepared by grinding the aluminum iso-propoxide in a blender followed by addition of a solution/dispersion of Iron (II) acetate. H.sub.3 PO.sub.4 was added to this mixture and the resulting mixture blended to form a homogeneous mixture. LUDOX-LS was added to this mixture except that in examples 13C to 16C the LUDOX-LS was added with the H.sub.3 PO.sub.4. The resulting mixtures were blended until a homogeneous mixture was observed. Organic templating agent was added to each mixture and the resulting mixtures placed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated, washed and the product recovered as in part (a) of this example. The products were analyzed and the observed FeAPSO products reported in Table I-C. The number of moles of each component in the reaction mixture was as follows:
______________________________________ Component Moles______________________________________ Al.sub.2 O.sub.3 0.9 P.sub.2 O.sub.5 0.9 SiO.sub.2 0.2 FeO* 0.2 Template 1.0 H.sub.2 O 50______________________________________ *Iron (II) acetate reported as Iron (II) oxide.
(c) Two reaction mixtures, designated Examples AC and BC in Table I-C, did not show FeAPSO products when analyzed by X-ray. Examples AC and BC followed the same procedure employed for Examples 5C and 6C.
TABLE I-C______________________________________ FeAPSOExample Template Temp (.degree.C.) Time (hr.) Product.sup.1______________________________________ 1C TEAOH 150 64 FeAPSO-34; FeAPSO-5 2C TEAOH 150 158 FeAPSO-34; FeAPSO-5 3C TEAOH 200 64 FeAPSO-34; FeAPSO-5 4C TEAOH 200 158 FeAPSO-34; FeAPSO-5 5C TEAOH 150 40 FeAPSO-34; FeAPSO-5 6C TEAOH 150 161 FeAPSO-34; FeAPSO-5 7C Pr.sub.2 NH .sup. 150 50 FeAPSO-11 8C Pr.sub.2 NH .sup. 150 168 FeAPSO-11 9C Pr.sub.2 NH .sup. 200 50 FeAPSO-1110C Pr.sub.2 NH .sup. 200 168 FeAPSO-1111C Pr.sub.3 N 150 50 FeAPSO-512C Pr.sub.3 N 150 168 FeAPSO-513C Pr.sub.3 N 200 50 FeAPSO-514C Pr.sub.3 N 200 168 FeAPSO-5 AC TEAOH 100 40 -- BC TEAOH 100 161 --______________________________________ .sup.1 Major species as identified by xray powder diffraction pattern of product, except that when two species where identified the first species listed is the major species observed. A "--" indicates no FeAPSO product was present as determined by Xray analysis.
EXAMPLES 15C to 19C
Examples 15C to 19C were carried out according to the general preparative procedure employed for examples 7C to 14C with examples 15C to 18C following the procedure employed for examples 7C to 10C and example 19C following the procedure followed for examples 11C to 14C. The reactive source of iron was Iron (II) sulfate instead of Iron (II) acetate. The temperature and time for the crystallization (digestion) procedure are set forth in Table II-C.
The number of moles of each component in the reaction mixtures for examples 15C to 18C was as follows:
______________________________________ Component Moles______________________________________ Al.sub.2 O.sub.3 0.9 P.sub.2 O.sub.5 0.9 SiO.sub.2 0.6 FeO* 0.2 Pr.sub.3 N 1.5 H.sub.2 O 50______________________________________ *Iron (II) sulfate reported as Iron (II) oxide.
The number of moles of each component in the reaction mixture of example 19C was as follows:
______________________________________ Component Moles______________________________________ Al.sub.2 O.sub.3 0.9 P.sub.2 O.sub.5 0.9 SiO.sub.2 0.2 FeO* 0.2 Pr.sub.3 N 1.0 H.sub.2 O 50______________________________________ *Iron (II) sulfate reported as Iron (II) oxide.
The products were subjected to analysis by x-ray and the observed FeAPSO products reported in Table II-C.
TABLE II-C______________________________________ FeAPSOExample Template Temp (.degree.C.) Time (hr.) Product.sup.1______________________________________15C Pr.sub.3 N 150 48 FeAPSO-516C Pr.sub.3 N 150 160 FeAPSO-517C Pr.sub.3 N 200 48 FeAPSO-518C Pr.sub.3 N 200 160 FeAPSO-519C Pr.sub.3 N 200 72 FeAPSO-5______________________________________ .sup.1 Major species as identified by xray powder diffraction pattern of product, except that when two species where identified the first species listed is the major species observed.
EXAMPLES 20C-27C
Examples 20C-27C were carried out according to the general preparative procedure employed for examples 1C to 8C using the following number of moles of each component in the reaction mixture:
______________________________________ Component Moles______________________________________ Al.sub.2 O.sub.3 0.9 P.sub.2 O.sub.5 0.9 SiO.sub.2 * 0.2, 0.6 FeO** 0.2 Template 1.0 H.sub.2 O 50______________________________________ *0.2 moles in examples 20C to 23C and 0.6 moles in examples 24C to 27C **Iron (II) acetate reported as Iron (II) oxide.
The temperature and time for the crystallization procedure and the observed FeAPSO products are reported in Table III-C.
TABLE III-C______________________________________ FeAPSOExample Template Temp (.degree.C.) Time (hr.) Product.sup.1______________________________________20C Quin 150 64 FeAPSO-1621C Quin 150 158 FeAPSO-16; FeAPSO-3522C Quin 200 64 FeAPSO-16; FeAPSO-3523C Quin 200 158 FeAPSO-16; FeAPSO-3524C MQuin 100 49 FeAPSO-1625C MQuin 100 161 FeAPSO-1626C MQuin 150 49 FeAPSO-16; FeAPSO-3527C MQuin 150 161 FeAPSO-16; FeAPSO-35______________________________________ .sup.1 Major species as identified by xray powder diffraction pattern of product, except that when two species were identified the first species listed is the major species observed.
EXAMPLES 28C AND 29C
Examples 28C and 29C were carried out according to the procedure of examples 13C to 16C, except that Iron (II) sulfate, was employed as the reactive iron source instead of Iron (II) acetate. The number of moles of each component in the reaction mixture for each example was as follows:
______________________________________ Component Moles______________________________________ Al.sub.2 O.sub.3 0.8 P.sub.2 O.sub.5 1.0 SiO.sub.2 0.4 FeO* 0.4 Template 2.0 H.sub.2 O 83______________________________________ *Iron (II) sulfate reported here as FeO
Examples CC and DC followed the procedure for Examples 28C and 29C. X-ray analysis of the reaction products did not show FeAPSO products.
The temperature and time for the crystallization procedure and the observed FeAPSO products are reported in Table IV-C.
TABLE IV-C______________________________________ FeAPSOExample Template Temp (.degree.C.) Time (hr.) Product.sup.1______________________________________28C TBAOH 200 49 FeAPSO-529C TBAOH 200 161 FeAPSO-5CC TBAOH 150 49 --DC TBAOH 150 161 --______________________________________ .sup.1 Major species as identified by xray powder diffraction pattern of product, except that when two species where identified the first species listed is the major species observed. A "--" indicates no FeAPSO product was present as determined by Xray analysis.
EXAMPLES 30C TO 43C
Examples 30C to 43C were carried out according to the procedure employed for examples 1C to 8C except that in examples 30C and 31C the aluminum source was CATAPAL and in examples 33C to 36C and 43C a seed crystal of a topologically similar molecular sieve was employed. The number of moles of each component in the reaction mixture in examples 30C to 43C was:
______________________________________ Component Moles______________________________________ Al.sub.2 O.sub.3 0.9 P.sub.2 O.sub.5 0.9 SiO.sub.2 0.2** FeO* 0.2 Template 1.0** H.sub.2 O 50______________________________________ *Iron (II) acetate reported here as FeO **SiO.sub.2 was 0.6 in example 32C and was 2.0 moles of template in examples 37C to 40C.
The template, temperature, time for the crystallization procedure and the observed FeAPSO products are reported in Table V-C.
TABLE V-C______________________________________ FeAPSOExample Template Temp (.degree.C.) Time (hr.) Product.sup.1______________________________________30C TMAOH 150 42 FeAPSO-2031C TMAOH 150 132 FeAPSO-2032C C-hex .sup. 220 114 FeAPSO-5; FeAPSO-4433C Pr.sub.2 NH .sup. 150 47 FeAPSO-3134C Pr.sub.2 NH .sup. 150 182 FeAPSO-3135C Pr.sub.2 NH .sup. 200 47 FeAPSO-3136C Pr.sub.2 NH .sup. 200 158 FeAPSO-3137C Pr.sub.2 NH .sup. 150 182 FeAPSO-4638C Pr.sub.2 NH .sup. 150 182 FeAPSO-4639C Pr.sub.2 NH .sup. 150 47 FeAPSO-5; FeAPSO-3440C Pr.sub.2 NH .sup. 200 158 FeAPSO-11; FeAPSO-3141C Pr.sub.2 N 150 42 FeAPSO-542C Pr.sub.2 N 150 132 FeAPSO-543C Pr.sub.2 N 150 42 FeAPSO-5EC Pr.sub.2 NH .sup. 150 47 --______________________________________ .sup.1 Major species as identified by xray powder diffraction pattern of product, except that when two species where identified the first species listed is the major species observed. A "--" indicates no FeAPSO product was present as determined by Xray analysis.
EXAMPLE 44C
(a) Samples of FeAPSO products were calcined at 600.degree. C. in air for 2 hours to remove at least part of the organic templating agent, except that FeAPSO-5 and FeAPSO-11 were calcined for 2.25 hours. The example in which the FeAPSO was prepared is indicated in parenthesis. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum at 350.degree. C. prior to measurement. The McBain-Bakr data for the FeAPSO compositions are set forth hereinafter.
(b) FeAPSO-5 (example 12C):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed______________________________________O.sub.2 3.46 100 -183 9.7O.sub.2 3.46 734 -183 11.6neopentane 6.2 100 24.5 3.8cyclohexane 6.0 59 23.7 5.7H.sub.2 O 2.65 4.6 23.9 10.7H.sub.2 O 2.65 20.0 23.6 19.2______________________________________
The above data demonstrate that the pore size of the calcined product is greater than 6.2 .ANG..
(c) FeAPSO-11 (example 10C):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed______________________________________O.sub.2 3.46 100 -183 7.6O.sub.2 3.46 734 -183 9.2neopentane 6.2 100 24.5 0.2cyclohexane 6.0 59 23.7 4.2H.sub.2 O 2.65 4.6 23.9 10.8H.sub.2 O 2.65 20.0 23.6 16.7______________________________________
The above data demonstrate that the pore size of the calcined product is about 6.0 .ANG..
(d) FeAPSO-20 (example 31C):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed______________________________________O.sub.2 3.46 99 -183 1.5O.sub.2 3.46 749 -183 8.5H.sub.2 O 2.65 4.6 23.2 22.7H.sub.2 O 2.65 16.8 23.5 30.0______________________________________
The above data demonstrates that the pore size of the calcined product is about 3.0 .ANG..
(e) FeAPSO-31 (example 34C):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed______________________________________O.sub.2 3.46 99 -183 6.8O.sub.2 3.46 749 -183 11.6neopentane 6.2 100 23.4 3.6cyclohexane 6.0 57 23.4 6.9H.sub.2 O 2.65 4.6 23.2 6.5H.sub.2 O 2.65 16.8 23.5 21.3______________________________________
The above data demonstrates that the pore size of the calcined product is greater than about 6.2 .ANG..
(f) FeAPSO-46 (example 38C):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed______________________________________O.sub.2 3.46 100 -183 2.6O.sub.2 3.46 749 -183 11.7neopentane 6.2 100 23.4 1.1cyclohexane 6.0 57 23.4 6.4H.sub.2 O 2.65 4.6 23.2 7.2H.sub.2 O 2.65 16.8 23.5 13.0______________________________________
The above data demonstrates that the pore size of the calcined product is greater than about 6.2 .ANG..
EXAMPLE 45C
Samples of FeAPSO products were subjected to chemical analysis as follows:
(a) The chemical analysis for FeAPSO-5 (example 12C) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 32.2P.sub.2 O.sub.5 45.4FeO 4.7SiO.sub.2 1.9Carbon 4.9LOI* 14.6______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.14R:0.21 FeO; 1.0 Al.sub.2 O.sub.3 :1.01 P.sub.2 O.sub.5 :0.10 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.03R(Fe.sub.0.05 Al.sub.0.46 P.sub.0.47 Si.sub.0.02)O.sub.2
(b) The chemical analysis of FeAPSO-11 (example 10C) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 33.2P.sub.2 O.sub.5 48.8FeO 4.5SiO.sub.2 2.4Carbon 5.1LOI* 9.8______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.22R:0.19FeO; 1.0 Al.sub.2 O.sub.3 ; 1.06 P.sub.2 O.sub.5 ; 0.08 SiO.sub.2 ; and a formula (anhydrous basis) of: 0.05(Fe.sub.0.04 Al.sub.0.45 P.sub.0.48 Si.sub.0.03)O.sub.2
(c) The chemical analysis of FeAPSO-20 (example 31C) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 29.1P.sub.2 O.sub.5 42.0FeO 4.8SiO.sub.2 2.5Carbon 7.6LOI* 19.7______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.55R:0.23FeO; 1.0 Al.sub.2 O.sub.3 ; 1.04 P.sub.2 O.sub.5 ; 0.15 SiO.sub.2 ; and a formula (anhydrous basis) of: 0.12(Fe.sub.0.05 Al.sub.0.45 P.sub.0.47 Si.sub.0.03)O.sub.2
(d) The chemical analysis of FeAPSO-31 (example 34C) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 34.7P.sub.2 O.sub.5 45.3FeO 4.2SiO.sub.2 1.6Carbon 3.4LOI* 12.9______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.14R:0.17FeO; 1.0 Al.sub.2 O.sub.3 ; 0.94 P.sub.2 O.sub.5 ; 0.08 SiO.sub.2 ; and a formula (anhydrous basis) of: 0.03(Fe.sub.0.04 Al.sub.0.49 P.sub.0.45 Si.sub.0.02)O.sub.2
EXAMPLE 46C
EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on clear crystals of FeAPSO products of the hereinafter designated examples. Analysis of crystals having a morphology characteristic of FeAPSO-5, FeAPSO-11, FeAPSO-20, FeAPSO-31, FeAPSO-34 and FeAPSO-46 gave the following analysis based on relative peak heights:
______________________________________ Average of Spot Probes______________________________________(a) FeAPSO-5 (example 12C):Fe 0.02Al 0.44P 0.52Si 0.02(b) FeAPSO-11 (example 10C):Fe 0.03Al 0.42P 0.52Si 0.03(c) FeAPSO-20 (example 31C):Fe 0.04Al 0.42P 0.49Si 0.05(d) FeAPSO-31 (example 34C):Fe 0.01Al 0.44P 0.48Si 0.06(e) FeAPSO-34 (example 3C):Fe 0.04Al 0.43P 0.45Si 0.07(f) FeAPSO-46 (example 38C):Fe 0.05Al 0.40P 0.43Si 0.12______________________________________
EXAMPLE 47C
(a) FeAPSO-5, as prepared in example 12C, was subjected to x-ray analysis. FeAPSO-5 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________7.4 11.95 1008.0* 11.05 412.6* 7.03 1313.0 6.81 714.95 5.93 1516.0* 5.54 <116.5* 5.37 117.1* 5.19 118.4* 4.82 <119.8 4.48 3320.3* 4.37 521.1 4.21 2722.0* 4.04 sh22.4 3.969 3822.6* 3.934 sh24.7 3.604 225.1* 3.548 125.9 3.440 1527.2* 3.278 128.0* 3.187 228.4* 3.143 129.0 3.079 630.0 2.979 1931.8* 2.814 333.7 2.660 234.5 2.600 935.2* 2.550 137.0 2.564 137.8 2.380 441.6 2.171 142.3 2.137 242.9 2.108 143.6 2.076 145.0 2.015 145.7* 1.985 147.7 1.907 351.5 1.774 155.6 1.653 1______________________________________ *peak contains impurity
(b) A portion of the as-synthesized FeAPSO-5 of part (a) was calcined in air at a temperature beginning at 500.degree. C. and ending at 600.degree. C. over a period of 2.25 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________7.4 11.95 1007.9* 11.19 sh8.45* 10.46 3512.85 6.89 1814.8 5.99 815.5* 5.72 1316.4* 5.40 217.0* 5.22 519.75 4.50 3120.2* 4.40 1421.1 4.21 3321.4* 4.15 sh22.0* 4.04 sh22.45 3.960 8323.8* 3.739 124.8 3.59 225.1* 3.548 225.95 3.434 3127.0* 3.302 227.9* 3.198 329.05 3.074 1430.05 2.974 2231.5* 2.840 2931.65 2.827 534.55 2.596 1535.0* 2.564 336.1* 2.488 137.0 2.430 437.8 2.380 838.2* 2.356 239.2* 2.298 240.2* 2.151 242.3 2.137 243.0 2.103 143.8 2.067 245.2 2.006 246.6* 1.949 247.7 1.907 451.6 1.771 455.6 1.653 2______________________________________ *peak contains impurity
(c) The FeAPSO-5 compositions are generally characterized by the data of Table VI-C below:
TABLE VI-C______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________7.3-7.5 12.11-11.79 m-vs 14.8-14.95 5.99-5.93 w-m19.6-19.8 4.53-4.48 m21.0-21.2 4.23-4.19 m22.35-22.5 3.98-3.95 m-vs 25.8-25.95 3.453-3.434 w-m______________________________________
(d) The FeAPSO-5 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the x-ray powder diffraction pattern shown in Table VII-C, below:
TABLE VII-C______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________7.3-7.5 12.11-11.79 55-10012.8-13.0 6.92-6.81 7-18 14.8-14.95 5.99-5.93 17-2719.6-19.8 4.53-4.48 24-6021.0-21.2 4.23-4.19 27-5322.35-22.5 3.98-3.95 38-100 24.7-24.85 3.604-3.583 0-6 25.8-25.95 3.453-3.434 15-6828.85-29.05 3.095-3.074 6-24 29.8-30.05 2.998-2.974 9-2733.45-33.7 2.679-2.660 2-10 34.4-34.55 2.607-2.596 8-1736.9-37.0 2.436-2.564 1-737.65-37.9 2.389-2.374 4-1341.4-41.6 2.181-2.171 0-442.1-42.3 2.146-2.137 0-442.6-43.1 2.122-2.099 0-443.5-43.8 2.080-2.067 0-444.9-45.2 2.019-2.006 0-747.6-47.7 1.910-1.907 0-551.3-51.6 1.781-1.771 0-455.4-55.6 1.658-1.653 1-6______________________________________
EXAMPLE 48C
(a) FeAPSO-11, as prepared in example 10C, was subjected to x-ray analysis. FeAPSO-11 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.1 10.92 319.45 9.36 4713.15 6.73 1515.7 5.64 3416.2 5.47 519.0 4.67 620.3 4.37 4321.0 4.23 10022.1 4.022 6222.5* 3.952 sh22.65 3.926 6123.1 3.850 8624.7 3.604 1026.4 3.376 2528.2** 3.164 sh28.6 3.121 1729.0 3.079 sh29.5 3.028 731.5 2.840 932.7 2.755 1933.6** 2.667 234.1 2.629 936.3 2.415 637.7 2.386 1439.2 2.298 542.9 2.108 544.7 2.027 650.6 1.804 554.7 1.678 555.5 1.656 3______________________________________ *peak may contain impurity **impurity peak
(b) A portion of the as-synthesized FeAPSO-11 of part (a) was calcined in air at 600.degree. C. for about 2.25 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.05 10.98 609.5 9.31 7212.9** 6.86 sh13.1 6.76 2013.7** 6.46 314.7** 6.03 315.9 5.57 5516.1 5.51 sh17.6** 5.04 319.9** 4.46 sh20.3 4.37 2821.3 4.17 10021.9* 4.06 sh22.4 3.969 8823.0* 3.867 sh23.4 3.802 7024.0** 3.708 324.4** 3.648 525.0* 3.562 425.8* 3.453 726.5 3.363 2027.7** 3.220 529.0 3.079 sh29.6 3.018 2030.4* 2.940 731.8 2.814 1032.7 2.739 1834.1 2.629 534.5** 2.600 435.6* 2.522 436.2 2.481 438.0 2.368 1043.3 2.090 344.8 2.023 549.0* 1.859 349.6* 1.838 354.6 1.681 355.7* 1.650 3______________________________________ *peak may contain impurity **impurity peak
(c) The FeAPSO-11 compositions are generally characterized by the data of Table VIII-C below:
TABLE VIII-C______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________8.05-8.1 10.98-10.92 m-s9.4-9.5 9.41-9.31 m21.0-21.3 4.23-4.17 vs22.1-22.4 4.022-3.969 m-s22.65-23.1 3.926-3.850 vw-m23.1-23.4 3.850-3.802 m-s______________________________________
(d) The FeAPSO-11 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the x-ray powder diffraction pattern shown in Table IX-C, below:
TABLE IX-C______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.05-8.1 10.98-10.92 30-809.4-9.5 9.41-9.31 47-7813.05-13.2 6.78-6.71 13-2415.7-15.9 5.64-5.57 33-5416.15-16.3 5.49-5.44 0-6 18.9-19.05 4.70-4.66 0-620.2-20.4 4.40-4.35 30-4321.0-21.3 4.23-4.17 10021.9 4.06 sh22.1-22.4 4.022-3.969 54-8622.5-22.6 3.952-3.934 sh22.65-23.1 3.926-3.850 sh-6123.1-23.4 3.850-3.802 48-8624.4-24.5 3.648-3.633 sh-624.7-24.9 3.604-3.576 0-1026.4-26.5 3.376-3.363 15-2528.6-28.8 3.121-3.100 17-1928.9-29.0 3.079-3.089 sh29.5-29.6 3.028-3.018 7-2131.5-31.8 2.840-2.814 8-12 32.7-32.85 2.755-2.726 13-19 34.1-34.25 2.629-2.618 5-936.2-36.5 2.481-2.462 5-737.6-38.0 2.392-2.368 7-1439.2-39.4 2.298-2.287 2-542.9-43.2 2.108-2.094 3-544.7-44.9 2.027-2.019 3-648.3-48.4 1.884-1.881 0-250.5-50.9 1.807-1.794 0-554.5-54.8 1.684-1.675 0-555.4-55.6 1.658-1.653 0-3______________________________________
EXAMPLE 49C
(a) FeAPSO-16, as prepared in example 21C, was subjected to x-ray analysis. FeAPSO-16 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 8.6** 10.28 710.9** 8.12 sh11.3 7.83 5813.2** 6.71 815.8** 5.61 2 17.25** 5.14 2117.7** 5.01 218.65 4.76 4020.3** 4.37 sh20.7** 4.29 sh21.1** 4.21 sh21.85 4.07 10022.9 3.883 1023.6** 3.770 225.0** 3.562 125.8** 3.453 126.5 3.363 2227.1** 3.290 sh28.6** 3.121 sh28.9 3.089 929.7 3.008 2432.0** 2.797 1032.6 2.747 434.6* 2.592 835.6** 2.522 137.85 2.377 839.7 2.270 344.3 2.045 248.45* 1.879 749.4** 1.845 251.4** 1.778 152.4 1.746 154.8* 1.675 2______________________________________ *peak may contain impurity **impurity peak
(b) The FeAPSO-16 compositions are generally characterized by the data of Table X-C below:
TABLE X-C______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________11.3-11.4 7.83-7.76 m18.55-18.75 4.78-4.73 m21.85-22.0 4.07-4.04 vs26.45-26.6 3.370-3.351 w-m29.6-29.8 3.018-2.998 w-m______________________________________
(c) The FeAPSO-16 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XI-C, below:
TABLE XI-C______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________11.3-11.4 7.83-7.76 38-6318.55-18.75 4.78-4.73 31-6321.85-22.0 4.07-4.04 10022.9 3.883 sh-1026.45-26.6 3.370-3.351 18-2628.9-29.0 3.089-3.079 0-1329.6-29.8 3.018-2.998 17-3032.4-32.8 2.763-2.730 0-1334.5-34.6 2.600-2.592 0-1037.65-37.9 2.389-2.374 0-1039.5-39.7 2.281-2.270 0-644.1-44.5 2.054-2.036 0-648.2-48.5 1.888-1.877 0-852.0-52.4 1.759-1.746 0-354.4-54.8 1.687-1.675 0-3______________________________________
EXAMPLE 50C
(a) FeAPSO-20, as prepared to in example 31C, was subjected to x-ray analysis. FeAPSO-20 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________14.0 6.32 59 19.85 4.47 47 22.25 3.998 4 24.35 3.654 10028.2 3.164 1631.6 2.831 1234.7 2.584 1637.6 2.394 240.3 2.240 4 42.85 2.110 5 47.65 1.909 452.0 1.758 8______________________________________
(b) A portion of the as-synthesized FeAPSO-20 of part (a) was calcined in air heating the sample from 500.degree. C. to 600.degree. C. over a period of 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________7.05* 12.56 67.5* 11.82 614.05 6.31 10020.02 4.43 2822.6 3.935 623.85* 3.733 524.5 3.635 4528.4 3.143 1131.7 2.823 1134.8 2.578 9______________________________________ *impurity peak
(c) The FeAPSO-20 compositions are generally characterized by the data of Table XII-C below:
TABLE VI-C______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________13.95-14.0 6.34-6.33 m-vs19.8-20.0 4.48-4.44 m24.3-24.5 3.663-3.633 m-vs28.15-28.4 3.169-3.143 w31.6-31.7 2.831-2.823 w34.7-34.8 2.585-2.578 w______________________________________
(d) The FeAPSO-20 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XIII-C, below:
TABLE XIII-C______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________13.95-14.0 6.34-6.33 57-10019.8-20.0 4.48-4.44 28-4722.25-22.6 3.998-3.935 3-624.3-24.5 3.663-3.633 45-10028.15-28.4 3.169-3.143 11-1631.6-31.7 2.831-2.823 11-1234.7-34.8 2.585-2.578 9-1637.6 2.392 2-340.2-40.3 2.242-2.240 4 42.7-42.85 2.114-2.110 547.5-47.6 1.914-1.909 3-452.0 1.759 8______________________________________
EXAMPLE 51C
(a) FeAPSO-31, as prepared in example 34C, was subjected to x-ray analysis. FeAPSO-31 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 8.5 10.41 64 9.45* 9.35 513.0 6.81 114.6 6.07 115.7 5.64 3 17.05 5.20 618.3 4.85 3 20.25 4.39 49 21.05* 4.22 9 21.95 4.05 3222.6 3.936 10023.2 3.833 625.1 3.546 4 25.65 3.474 4 26.45 3.372 227.9 3.195 1328.7 3.110 129.7 3.008 731.7 2.821 2032.7 2.739 1 35.15 2.555 936.1 2.489 237.2 2.418 2 37.65 2.390 2 38.15 2.358 339.3 2.293 439.6 2.275 340.2 2.244 245.2 2.006 2 46.65 1.947 3 48.65 1.871 2 50.75 1.799 2 51.65 1.770 455.5 1.650 2______________________________________ *Peak may contain impurity
(b) A portion of the as-synthesized FeAPSO-31 of part (a) was calcined in air at 600.degree. C. for about 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 8.6 10.26 73 9.8* 9.04 3 12.95 6.83 114.9 5.95 516.2 5.46 417.2 5.16 11 18.45 4.80 420.4 4.35 50 22.15 4.016 44 22.75 3.909 100 23.45 3.795 325.3 3.521 525.8 3.449 928.1 3.174 1329.9 2.990 12 31.1** 2.876 231.9 2.806 3032.7 2.739 235.3 2.542 1036.3 2.475 5 37.35 2.407 3 37.85 2.378 2 38.35 2.346 339.5 2.282 4 40.35 2.234 3 44.15 2.052 2 45.05* 2.013 245.4 1.997 2 46.85 1.940 5 47.65 1.909 248.9 1.863 349.3 1.848 2 50.95 1.793 251.8 1.765 655.6 1.653 3______________________________________ *peak may contain impurity **impurity peak
(c) The FeAPSO-31 compositions are generally characterized by the data of Table XIV-C below:
TABLE XIV-C______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________8.5-8.6 10.40-10.28 w-s20.2-20.4 4.40-4.35 m21.1-21.2 4.21-4.19 w22.0-22.1 4.040-4.022 m22.6-22.7 3.934-3.917 vs31.7-31.9 2.822-2.805 w-m______________________________________
(d) The FeAPSO-31 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XV-C below:
TABLE XV-C______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.5-8.6 10.40-10.28 10-889.5-9.8 9.35-9.04 3-11 9.9 8.92 0-313.0-13.3 6.81-6.67 1-414.6-14.9 6.07-5.95 0-515.7-16.2 5.64-5.46 3-717.0-17.2 5.20-5.17 5-1118.3-18.5 4.84-4.80 2-420.2-20.4 4.40-4.35 36-5021.1-21.2 4.21-4.19 9-1822.0-22.1 4.040-4.022 26-4422.6-22.7 3.934-3.919 10023.2-23.4 3.833-3.795 3-1225.1-25.3 3.546-3.521 4-525.6-25.8 3.474-3.449 3-926.4-26.6 3.372-3.352 0-527.4-27.5 3.258-3.248 2-427.9-28.1 3.195-3.174 12-1428.3 3.152 0-328.7-28.8 3.111-3.103 0-329.7-29.9 3.008-2.990 6-1231.1 2.876 0-231.7-31.9 2.822-2.805 19-3032.7-33.0 2.739-2.718 0-335.1-35.3 2.555-2.542 9-1036.1-36.3 2.489-2.475 2-537.3-37.4 2.418-2.407 0-337.6-37.8 2.390-2.378 2-338.1-38.4 2.365-2.346 2-339.3-39.5 2.293-2.282 3- 439.6-39.7 2.275-2.271 0-340.2-40.3 2.244-2.239 0-344.1 2.052 0-244.9 2.020 0-245.0-45.1 2.015-2.012 0-245.2-45.4 2.006-1.997 2-346.6-46.8 1.947-1.940 3-547.5-47.6 1.914-1.909 0-248.6-48.9 1.872-1.863 2-349.1-49.3 1.854-1.848 0-350.8-50.9 1.799-1.793 0-251.6-51.8 1.771-1.765 0-455.5-55.6 1.657-1.653 0-3______________________________________
EXAMPLE 52C
(a) FeAPSO-34, as prepared in example 3C, was subjected to x-ray analysis. FeAPSO-34 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 7.3* 12.1 5 9.35 9.5 10012.7 7.0 1014.0 6.3 8 14.8* 5.99 215.9 5.57 3217.9 4.96 7 19.6* 4.53 3 (sh)20.4 4.35 5022.3 3.99 622.9 3.88 225.1 3.548 1025.7 3.466 1127.5 3.243 228.2 3.164 229.4 3.038 2 (sh)30.4 2.940 1931.1 2.876 1234.4 2.607 436.2 2.481 239.5 2.281 243.3 2.090 347.5 1.914 248.9 1.863 351.0 1.791 253.0 1.728 254.5 1.684 1______________________________________ *Impurity peak
(b) A portion of the as-synthesized FeAPSO-34 of part (a) was calcined in air at 600.degree. C. for about 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 7.5* 11.79 7 9.6 9.21 10013.0 6.81 1716.2 5.47 916.9 5.25 118.0 4.93 519.3 4.60 5 19.9* 4.46 220.9 4.25 17 22.55 3.943 723.4 3.802 224.2 3.678 225.1 3.548 526.2 3.401 7 27.2* 3.278 128.2 3.164 229.2 3.058 231.0 2.885 16______________________________________ *Impurity peak
(c) The FeAPSO-34 compositions are generally characterized by the data of Table XVI-C below:
TABLE XVI-C______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________9.35-9.7 9.46-9.12 vs12.7-13.0 6.97-9.81 w-m15.9-16.2 5.57-5.47 w-m20.4-20.9 4.35-4.25 w-s22.3-22.5 3.99-3.95 vw--s25.7-26.2 3.466-3.401 vw-m______________________________________
(d) The FeAPSO-34 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XVII-C below:
TABLE XVII-C______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________9.35-9.7 9.46-9.12 10012.7-13.0 6.97-6.81 10-2513.9-14.1 6.37-6.28 2-1115.9-16.2 5.57-5.47 9-4717.6-18.0 5.04-4.93 5-1618.9-19.3 4.70-4.60 0-520.4-20.9 4.35-4.25 17-8922.3-22.5 3.99-3.95 4-8822.9-23.4 3.88-3.52 2-824.8-25.3 3.59-3.52 5-1825.7-26.2 3.466-3.401 7-3227.5-27.6 3.243-3.232 0-528.0-28.4 3.187-3.143 1-329.4-29.6 3.038-3.018 0-4 (sh)30.4-30.6 2.940-2.922 0-2831.0-31.2 2.885-2.867 2 (sh)-1732.4 2.763 0-134.4-34.6 2.607-2.592 0-1335.9-36.3 2.501-2.475 0-339.5-39.6 2.281-2.276 0-343.3-43.4 2.090-2.085 0-447.5-47.6 1.914-1.910 0-548.6-49.1 1.873-1.855 0-750.6-51.1 1.804-1.787 0-353.0-53.2 1.728-1.722 0-354.5-54.6 1.684-1.681 0-1______________________________________
EXAMPLE 53C
(a) FeAPSO-35, as prepared in example 27C, was subjected to x-ray analysis. FeAPSO-35 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 8.7 10.19 511.0 8.03 sh 11.4** 7.77 5113.5 6.57 916.0 5.55 317.4 5.09 2817.9 4.95 5 18.65** 4.76 5021.0 4.22 1521.9 4.06 100 22.9** 3.885 9 23.45 3.793 825.1 3.548 3 26.5** 3.365 25 27.15 3.285 728.6 3.118 16 28.9* 3.091 (sh) 29.7** 3.010 2732.2 2.780 (sh) 32.5** 2.754 1334.6 2.591 7 37.8* 2.381 10 44.1** 2.053 3 48.25* 1.886 851.6 1.774 1 52.15** 1.754 2 54.5** 1.684 3______________________________________ *peak may contain impurity **impurity peak
(b) The FeAPSO-35 compositions are generally characterized by the data of Table XVIII-C below:
TABLE XVIII-C______________________________________2- d, (.ANG.) Relative Intensity______________________________________10.9-11.1 8.12-7.97 vw-m13.2-13.5 6.71-6.56 vw-w17.2-17.4 5.16-5.10 w-m21.85-22.0 4.07-4.04 vs23.2-23.8 3.834-3.739 vw-m 32.0-32.25 2.797-2.776 vw-m______________________________________
(c) The FeAPSO-35 compositions are generally characterized by the x-ray powder diffraction pattern shown in Table XIX-C, below:
TABLE XIX-C______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.6-8.7 10.28-10.19 0-1410.9-11.1 8.12-7.97 sh-3813.2-13.5 6.71-6.56 7-1915.8-16.2 5.61-5.47 1-617.2-17.4 5.16-5.10 11-4117.75-17.9 5.00-4.95 sh-8 20.8-21.25 4.27-4.18 sh-1521.85-22.0 4.07-4.040 10023.2-23.8 3.834-3.739 0-2024.9-25.1 3.576-3.548 0-3 26.9-27.15 3.314-3.285 0-15 28.5-28.65 3.132-3.114 sh-1628.8-29.0 3.100-3.082 0-sh 32.0-32.25 2.797-2.776 sh-2434.5-34.9 2.600-2.571 3-837.7-38.1 2.386-2.362 6-10______________________________________
EXAMPLE 54C
(a) FeAPSO-44, as prepared in example 32C, was subjected to x-ray analysis. FeAPSO-44 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 7.5** 11.80 6709.5 9.29 9412.95* 6.83 70 14.95** 5.92 13216.15 5.48 3017.4 5.10 719.0 4.67 719.8** 4.48 32621.0* 4.23 33221.8 4.07 34 22.45** 3.963 63123.1 3.850 724.5 3.635 10024.7** 3.604 4026.0* 3.425 193 27.15** 3.283 3028.05* 3.180 19 29.05** 3.075 11030.1* 2.966 13730.9 2.894 4033.0 2.714 7 33.65** 2.664 3734.6** 2.591 10535.55 2.525 12837.0** 2.430 28 37.65** 2.389 8242.3* 2.137 2342.55* 2.125 1743.7* 2.072 1545.1** 2.011 1447.75* 1.904 3651.6** 1.77 1752.0** 1.758 1655.8** 1.647 19______________________________________ *peak might contain impurity **impurity peak
(b) The FeAPSO-44 compositions are generally characterized by the data of Table XX-C below:
TABLE XX-C______________________________________2.theta. d, (.ANG.) Relative Intensity*______________________________________9.5 9.31 m12.95 6.83 m16.15 5.49 vw21.0 4.23 vs24.5 3.631 m30.9 2.894 w______________________________________ *peak intensities were low and may affect accuracy
(c) The FeAPSO-44 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXI-C below:
TABLE XXI-C______________________________________2.theta. d, (.ANG.) 100 .times. I/Io*______________________________________ 9.5 9.31 28 12.95 6.83 21 16.15 5.49 917.4 5.10 219.0 4.67 221.0 4.23 10021.8 4.07 1023.1 3.850 224.5 3.635 3026.0 3.427 58 28.05 3.180 630.1 2.966 1130.9 2.894 1233.0 2.714 2 35.55 2.525 3942.3 2.137 7 42.55 2.125 543.7 2.072 5 47.75 1.904 11______________________________________ *peak intensities were low and may effect accuracy
EXAMPLE 55C
(a) FeAPSO-46, as prepared in example 38C was subjected to x-ray analysis. FeAPSO-46 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________6.6 13.42 3 7.75 11.38 100 12.45 7.11 213.2 6.70 213.8 6.41 115.0 5.91 1 15.35 5.77 116.7 5.31 217.3 5.13 <119.9 4.47 120.6 4.31 3 21.65 4.11 722.9 3.885 424.3 3.660 325.2 3.534 <1 26.95 3.307 3 27.85 3.206 2 28.35 3.147 1 28.85 3.093 3 29.95 2.985 130.2 2.959 <1 30.95 2.889 <1 31.35 2.855 231.8 2.814 <1 33.05 2.711 134.4 2.606 1 36.05 2.490 336.7 2.448 <139.9 2.259 <1 41.25 2.188 <144.2 2.049 1 47.85 1.902 150.4 1.811 <151.7 1.768 <152.5 1.743 <1______________________________________
(b) A portion of the as-synthesized FeAPSO-46 of part (a) was calcined in air at 500.degree. C. for about 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 6.85 12.92 9 8.0 11.04 10013.6 6.51 4 15.35 5.76 316.0 5.55 3 17.15 5.17 321.3 4.17 222.2 4.006 2 23.45 3.793 224.9 3.575 227.6 3.232 232.0 2.797 2______________________________________
(c) The FeAPSO-46 compositions are generally characterized by the data of Table XXII-C below.
TABLE XXII-C______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________6.6-6.8 13.39-13.00 vw7.8-8.0 11.33-11.05 vs13.2-13.6 6.71-6.51 vw21.65-22.2 4.10-4.00 vw 22.9-23.45 3.883-3.793 vw26.95-27.6 3.308-3.232 vw______________________________________
(d) The FeAPSO-46 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXIII-C below:
TABLE XXIII-C______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________6.6-6.8 13.39-13.00 3-97.8-8.0 11.33-11.05 10012.45-12.6 7.11-7.03 0-313.2-13.6 6.71-6.51 2-413.8-14.0 6.41-6.33 1-2 15.0-15.35 5.91-5.76 1-315.35-16.0 5.77-5.55 1-3 16.7-17.15 5.31-5.17 2-317.3 5.13 0-119.9-20.5 4.47-4.43 1-220.6-21.3 4.31-4.17 2-321.65-22.2 4.10-4.00 2-8 22.9-23.45 3.883-3.793 2-424.3-24.9 3.659-3.575 2-325.2 3.534 0-126.95-27.6 3.308-3.232 2-427.85-27.95 3.206-3.190 0-328.35-28.55 3.147-3.125 0-228.85-29.05 3.093-3.076 0-329.95-30.1 2.985-2.968 0-130.2 2.959 0-130.95 2.889 0-131.3-32.0 2.855-2.797 2 31.8-32.05 2.814-2.792 0-133.05 2.711 0-134.4 2.608 0-136.05-36.2 2.490-2.481 0-336.7 2.448 0-139.9 2.259 0-141.25 2.188 0-1 44.2-44.35 2.049-2.043 0-147.8-48.0 1.902-1.895 0-150.4 1.811 0-151.7 1.768 0-152.5 1.743 0-1______________________________________
EXAMPLE 56C
In order to demonstrate the catalytic activity of the FeAPSO compositions, calcined samples of FeAPSO products were tested for the catalytic cracking of n-butane using a bench-scale apparatus.
The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm I.D. In each test the reactor was loaded with particles of the selected FeAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The samples had been previously calcined in air or nitrogen to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500.degree. C. for one hour. The feedstock was a helium and n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.
The pseudo-first-order rate constant (k.sub.A) was calculated to determine the relative catalytic activity of the FeAPSO compositions. The k.sub.A value (cm.sup.3 /g min) obtained for the FeAPSO compositions are set forth, below, in Table XXIV-C:
TABLE XXIV-C______________________________________FeAPSO ofExample No:.sup.1 Rate Constant (k.sub.A)______________________________________FeAPSO-5 (Ex. 12 C) 0.5FeAPSO-11 (Ex. 10 C) 0.7FeAPSO-31 (Ex. 34 C) 1.3FeAPSO-46 (Ex. 37 C) 0.9______________________________________ .sup.1 FeAPSO were calcined as follows prior to being activated: (a)FeAPSO-5: at 600.degree. C. in air for 2 hours; (b)FeAPSO-11: at 600.degree. C. in air for 2.25 hours; (c)FeAPSO-31: at 500.degree. C. to 600.degree. C. in air for 2 hours; and (d)FeAPSO-46: heated from 100.degree. C. to 600.degree. C. in nitrogen over a 2hour period.
MANGANESE-ALUMINUM-PHOSPHORUS-SILICON-OXIDE MOLECULAR SIEVES
Molecular sieves containing manganese, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents
In the following examples the MnAPSO compositions were prepared using numerous reagents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea Corporation for hydrated pseudoboehmite;
(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO.sub.2 and 0.1 weight percent Na.sub.2 O;
(d) H.sub.3 PO.sub.4 : 85 weight percent aqueous phosphoric acid;
(e) MnAc: Manganese acetate, Mn (C.sub.2 H.sub.3 O.sub.2).sub.2.4H.sub.2 O;
(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(h) Pr.sub.2 NH: di-n-propylamine, (C.sub.3 H.sub.7).sub.2 NH;
(i) Pr.sub.3 N: tri-n-propylamine (C.sub.3 H.sub.7).sub.3 N;
(j) Quin: Quinuclidine, (C.sub.7 H.sub.13 N);
(k) MQuin: Methyl Quinuclidine hydroxide, (C.sub.7 H.sub.13 NCH.sub.3 OH);
(l) C-hex: cyclohexylamine;
(m) TMAOH: tetramethylammonium hydroxide;
(n) TPAOH: tetrapropylammonium hydroxide; and
(o) DEEA: 2-diethylaminoethanol.
PREPARATIVE PROCEDURES
The following preparative examples were carried out by forming a starting reaction mixture by adding the H.sub.3 PO.sub.4 to one half of the quantity of water. This mixture was mixed and to this mixture the aluminum isopropoxide or CATAPAL was added. This mixture was then blended until a homogeneous mixture was observed. To this mixture the LUDOX LS was added and the resulting mixture blended (about 2 minutes) until a homogeneous mixture was observed. A second mixture was prepared using the manganese acetate and the remainder (about 50%) of the water. The two mixtures were admixed and the resulting mixture blended until a homogeneous mixture was observed. The organic templating agent was then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture was observed, i.e., about 2 to 4 minutes. (The pH of the mixture was measured and adjusted for temperature). The mixture was then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150.degree. C. or 200.degree. C.) for a time or placed in lined screw top bottles for digestion at 100.degree. C. All digestions were carried out at the autogeneous pressure.
The molar composition for each preparation will be given by the relative moles of the components of the reaction mixture with H.sub.3 PO.sub.4 and MnAc are given respectively in terms of P.sub.2 O.sub.5 and MnO content of the reaction mixture.
The following examples are provided to further illustrate the invention and are not intended to be limiting thereof:
EXAMPLES 1D TO 64D
MnAPSO molecular sieves were prepared according to the above identified procedure and the MnAPSO products determined by X-ray analysis. The results of examples 1D to 64D are set forth in Tables I-D to IV-D.
TABLE I-D______________________________________ MnAPSOExample.sup.1 Template Temp (.degree.C.) Time (days) Product.sup.2______________________________________ 1D TEAOH 150 4 MnAPSO-34; MnAPSO-5 2D TEAOH 150 11 MnAPSO-5; MnAPSO-34 3D TEAOH 200 4 MnAPSO-5; MnAPSO-34 4D TEAOH 200 11 MnAPSO-5; MnAPSO-34 5D TEAOH 100 2 --.sup.3 6D TEAOH 100 7 MnAPSO-34 7D TEAOH 150 2 MnAPSO-34; MnAPSO-5 8D TEAOH 150 7 MnAPSO-34; MnAPSO-5 9D TEAOH 200 2 MnAPSO-5; MnAPSO-3410D TEAOH 200 7 MnAPSO-5; MnAPSO-3411D TEAOH 100 14 MnAPSO-3412D TEAOH 150 14 MnAPSO-34; MnAPSO-513D TEAOH 200 14 MnAPSO-5; MnAPSO-34______________________________________ .sup.1 The reaction mixture comprised: 1.0 TEAOH: 0.2 MnO: 0.9 Al.sub.2 O.sub.3 : 0.9 P.sub.2 O.sub.5 : rSiO.sub.2 : 50 H.sub.2 O where "r" was 0.2 for examples 1D to 4D and was 0.6 for examples 5D to 13D. .sup.2 Major species as identified by xray powder diffraction pattern of product, except that when two species where identified the first species listed is the predominant species observed. .sup.3 No MnAPSO products were observed by xray analysis.
TABLE II-D______________________________________ MnAPSOExample.sup.1 Template Temp (.degree.C.) Time (days) Product.sup.2______________________________________14D Quin 150 4 MnAPSO-16; MnAPSO-3515D Quin 150 11 MnAPSO-16; MnAPSO-3516D Quin 200 4 MnAPSO-16; MnAPSO-3517D Quin 200 11 MnAPSO-16; MnAPSO-3518D Quin 100 4 MnAPSO-3519D Quin 100 11 MnAPSO-3520D MQuin 150 2 MnAPSO-35; MnAPSO-1621D MQuin 150 7 MnAPSO-3522D MQuin 200 2 MnAPSO-3523D MQuin 200 7 MnAPSO-3524D Pr.sub.2 NH 150 4 MnAPSO-1125D Pr.sub.2 NH 150 11 MnAPSO-1126D Pr.sub.2 NH 200 4 MnAPSO-11; MnAPSO-3927D Pr.sub.2 NH 200 11 MnAPSO-11; MnAPSO-3928D Pr.sub.2 NH 100 4 --.sup.329D Pr.sub.2 NH 100 11 --.sup.3______________________________________ .sup.1 The reaction mixture comprised: 1.0 R: 0.2 MnO: 0.9 Al.sub.2 O.sub.3 : 0.9 P.sub.2 O.sub.5 : 0.2 SiO.sub.2 : 50 H.sub.2 O where "R" is the template, as identified in Table IID. .sup.2 Major species as identified by xray powder diffraction pattern of product, except that when two species where identified the first species listed is the predominant species observed. .sup.3 No MnAPSO products were observed by xray analysis.
TABLE III-D______________________________________ MnAPSOExample.sup.1 Template Temp (.degree.C.) Time (days) Product.sup.2______________________________________30D Pr.sub.3 N .sup. 150 4 MnAPSO-531D Pr.sub.3 N .sup. 150 11 MnAPSO-532D Pr.sub.3 N .sup. 200 4 MnAPSO-533D Pr.sub.3 N .sup. 200 11 MnAPSO-534D Pr.sub.3 N .sup. 100 4 --.sup.335D Pr.sub.3 N .sup. 100 11 --.sup.336D TBAOH 150 4 --.sup.337D TBAOH 150 10 --.sup.338D TBAOH 200 4 MnAPSO-539D TBAOH 200 10 MnAPSO-540D C-hex .sup. 150 3 MnAPSO-1341D C-hex .sup. 150 9 MnAPSO-44; MnAPSO-1342D C-hex .sup. 200 3 MnAPSO-5; MnAPSO-4443D C-hex .sup. 200 9 MnAPSO-5; MnAPSO-44______________________________________ The reaction mixture comprised: (a)Examples 30D to 35D: 1.0 Pr.sub.3 N; 0.2 MnO; 0.9 Al.sub.2 O.sub.3 ; 0.9 P.sub.2 O.sub.5 ; 0.2 SiO.sub.2 ; 50 H.sub.2 O (b)Examples 36D to 39D: 2.0 TBAOH; 0.4 MnO; 0.8 Al.sub.2 O.sub.3 ; 1.0 P.sub.2 O.sub.5 ; 0.4 SiO.sub.2 ; 50 H.sub.2 O (c)Examples 40D to 43D: 1.0 Chex; 0.2 MnO; 0.9 Al.sub.2 O.sub.3 ; 0.9 P.sub.2 O.sub.5 ; 0.6 SiO.sub.2 ; 50 H.sub.2 O .sup.2 Major species as identified by xray powder diffraction pattern of product, except that when two species where identified the first species listed is the predominant species observed. .sup.3 No MnAPSO products were observed by xray analysis.
TABLE IV-D______________________________________ MnAPSOExample.sup.1 Template Temp (.degree.C.) Time (days) Product.sup.2______________________________________44D TPAOH 150 2 MnAPSO-545D TPAOH 200 2 MnAPSO-546D TMAOH 150 4 MnAPSO-2047D TMAOH 200 4 MnAPSO-2048D DEA 150 9 MnAPSO-4749D DEA 150 18 MnAPSO-47.sup. 50D.sup.4 Pr.sub.2 NH 150 4 MnAPSO-31.sup. 51D.sup.4 Pr.sub.2 NH 150 10 MnAPSO-31; MnAPSO-46.sup. 52D.sup.4 Pr.sub.2 NH 200 4 MnAPSO-31; MnAPSO-11.sup. 53D.sup.4 Pr.sub.2 NH 200 10 MnAPSO-31; MnAPSO-11.sup. 54D.sup.4 Pr.sub.2 NH 150 2 MnAPSO-31.sup. 55D.sup.4 Pr.sub.2 NH 150 2 MnAPSO-31.sup. 56D.sup.4 Pr.sub.2 NH 200 2 MnAPSO-31; MnAPSO-1157D Pr.sub.2 NH 200 25 MnAPSO-11; MnAPSO-5 MnAPSO-39; MnAPSO-4658D Quin 225 5 MnAPSO-16; MnAPSO-35.sup. 59D.sup.5 Pr.sub.3 N 150 2 MnAPSO-36.sup. 60D.sup.5 Pr.sub.3 N 150 7 MnAPSO-36; MnAPSO-5.sup. 61D.sup.5 Pr.sub.3 N 200 2 MnAPSO-36; MnAPSO-5.sup. 62D.sup.5 Pr.sub.3 N 200 7 MnAPSO-36; MnAPSO-563D C-hex 225 5 MnAPSO-5; MnAPSO-4464D C-hex 200 4 MnAPSO-44______________________________________ .sup.1 The reaction mixture comprised: 1.0 R; 0.2 MnO; 0.9 Al.sub.2 O.sub.3 ; 0.9 P.sub.2 O.sub.5 ; 0.6 SiO.sub.2 ; 50 H.sub.2 O where R is a above identified and except than in examples 48D, 49D, 57D and 64D the moles of "R" was 2.0 and in example 58D the coefficient for P.sub.2 O.sub.5 was 1.0 instead of 0.9. .sup.2 Major species as identified by xray powder diffraction pattern of product, except that when two species where identified the first species listed is the predominant species observed. .sup.3 No MnAPSO products were observed by xray analysis. .sup.4 Seed crystals of AlPO.sub.4 -31 were employed (U.S. Pat. No. 4,310,440). .sup.5 Seed crystals of MnAPO36 were employed, as disclosed in U.S. Ser. No. 514,334; filed July 15, 1983.
EXAMPLE 65D
(a) Samples of the MnAPSO products were calcined in air or nitrogen to remove at least part of the organic templating agent of the product. The example in which a given MnAPSO product was prepared is given in parenthesis. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum (less than 0.04 torr) at 350.degree. C. prior to measurement. The McBain-Bakr data for the aforementioned MnAPSO molecular sieves are set forth hereinafter:.
(a) MnAPSO-5 (Example 31D):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 102 -183 8.9O.sub.2 3.46 750 -183 10.8n-butane 4.3 504 23.0 4.4cyclohexane 6.0 65 23.4 5.4H.sub.2 O 2.65 4.6 23.0 8.1H.sub.2 O 2.65 19.5 23.0 17.1______________________________________ *MnAPSO-5 was calcined at 600.degree. C. in air for 4 hours.
The above data demonstrate that the pore size of the calcined MnAPSO-5 product is greater than about 6.2 .ANG..
(b) MnAPSO-11 (Example 24D):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 106 -183 7.0O.sub.2 3.46 744 -183 11.1neopentane 6.2 741 25.3 2.5isobutane 5.0 740 24.2 3.5cyclohexane 6.0 82 23.9 10.7H.sub.2 O 2.65 4.6 24.9 5.1H.sub.2 O 2.65 19 24.8 14.9______________________________________ *MnAPSO was calcined at 600.degree. C. in air for 2 hours.
The above data demonstrate that the pore size of the calcined MnAPSO-11 product is greater than about 6.0 .ANG..
(c) MnAPSO-20 (Example 46D):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 102 -183 0.7O.sub.2 3.46 744 -183 1.2H.sub.2 O 2.65 4.6 23.3 9.0H.sub.2 O 2.65 19 23.2 13.7______________________________________ *MnAPSO was calcined at 500.degree. C. in air for 1 hour.
The above data demonstrate that the pore size of the calcined MnAPSO-20 product is greater than about 2.65 .ANG. and less than about 3.46 .ANG..
(d) MnAPSO-31 (Example 55D):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 105 -183 5.6O.sub.2 3.46 741 -183 9.7Neopentane 6.2 739 23.5 4.6H.sub.2 O 2.65 4.6 23.8 5.8H.sub.2 O 2.65 20 24.0 15.5______________________________________ *MnAPSO-31 was calcined at 500.degree. C. in air for 1.5 hours.
The above data demonstrate that the pore size of the calcined MnAPSO-31 product is greater than about 6.2 .ANG..
(e) MnAPSO-34 (Example 11D):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 103 -183 11.4O.sub.2 3.46 731 -183 15.6isobutane 5.0 741 24.5 0.8n-hexane 4.3 103 24.4 4.6H.sub.2 O 2.65 4.6 24.4 15.2H.sub.2 O 2.65 18.5 23.9 24.4______________________________________ *MnAPSO-34 was calcined at 425.degree. C. in nitrogen for 2 hours.
The above data demonstrate that the pore size of the calcined MnAPSO-34 product is about 4.3 .ANG..
(f) MnAPSO-35 (Example 21D):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 103 -183 1.8O.sub.2 3.46 731 -183 2.6n-hexane 4.3 103 24.4 0.8H.sub.2 O 2.65 4.6 24.4 9.9H.sub.2 O 2.65 18.5 23.9 15.9______________________________________ *MnAPSO-35 was calcined at 500.degree. C. in nitrogen for 2 hours.
The above data demonstrate that the pore size of the calcined MnAPSO-35 product is about 4.3 .ANG..
(g) MnAPSO-44 (Example 64D):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 102 -183 18.2O.sub.2 3.46 744 -183 20.1n-hexane 4.3 95 23.6 1.3isobutane 5.0 746 24.1 0.5H.sub.2 O 2.65 4.6 24.8 22.7H.sub.2 O 2.65 19 29.8 27.7______________________________________ *MnAPSO-44 was calcined at 500.degree. C. in air for 1.0 hour.
The above data demonstrate that the pore size of the calcined MnAPSO-44 product about 4.3 .ANG..
EXAMPLE 66D
Samples of the as-synthesized products of certain examples were subjected to chemical analysis. The example in which a given MnAPSO was prepared is noted in parenthesis. The chemical analysis for these MnAPSOs was as follows:
(a) The chemical analysis for MnAPSO-5 (Example 31D) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 31.8P.sub.2 O.sub.5 46.4MnO 4.1SiO.sub.2 3.0Carbon 5.2LOI* 14.5______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.058 MnO; 0.312 Al.sub.2 O.sub.3 : 0.327 P.sub.2 O.sub.5 : 0.050 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.05R(Mn.sub.0.04 Al.sub.0.45 P.sub.0.47 Si.sub.0.04)O.sub.2
(b) The chemical analysis of MnAPSO-11 (Example 24D) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 32.5P.sub.2 O.sub.5 46.7MnO 4.3SiO.sub.2 2.1Carbon 4.1LOI* 14.0______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.061 MnO; 0.319 Al.sub.2 O.sub.3 ; 0.329 P.sub.2 O.sub.5 ; 0.035 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.06R(Mn.sub.0.04 Al.sub.0.46 P.sub.0.47 Si.sub.0.03)O.sub.2
(c) The chemical analysis for MnAPSO-20 (Example 46D) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 27.3P.sub.2 O.sub.5 39.6MnO 4.6SiO.sub.2 8.0Carbon 8.4LOI* 19.4______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.065 MnO; 0.268 Al.sub.2 O.sub.3 : 0.279 P.sub.2 O.sub.5 : 0.133 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.18R(Mn.sub.0.05 Al.sub.0.41 P.sub.0.43 Si.sub.0.10)O.sub.2
(d) The chemical analysis of MnAPSO-31 was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 31.8P.sub.2 O.sub.5 43.8MnO 3.2SiO.sub.2 2.6Carbon 2.9LOI* 16.7______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.058 MnO; 0.312 Al.sub.2 O.sub.3 ; 0.309 P.sub.2 O.sub.5 ; 0.043 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.04R(Mn.sub.0.04 Al.sub.0.47 P.sub.0.46 Si.sub.0.03)O.sub.2
(e) The chemical analysis of MnAPSO-34 (Example 6D) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 25.0P.sub.2 O.sub.5 35.8MnO 7.9SiO.sub.2 11.6Carbon 3.3LOI* 19.7______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.11 MnO; 0.25 Al.sub.2 O.sub.3 ; 0.19 P.sub.2 O.sub.5 ; 0.19 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.04R(Mn.sub.0.09 Al.sub.0.38 P.sub.0.39 Si.sub.0.15)O.sub.2
(f) The chemical analysis of MnAPSO-35 (Example 23D) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 25.2P.sub.2 O.sub.5 41.3MnO 7.1SiO.sub.2 4.2Carbon 12.8LOI* 21.3______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.100 MnO; 0.247 Al.sub.2 O.sub.3 ; 0.291 P.sub.2 O.sub.5 ; 0.07 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.13R(Mn.sub.0.08 Al.sub.0.40 P.sub.0.47 Si.sub.0.06)O.sub.2
(g) The chemical analysis of MnAPSO-36 (Example 59D) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 27.7P.sub.2 O.sub.5 37.2MnO 4.6SiO.sub.2 9.5Carbon 3.0LOI* 19.6______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios anhydrous basis) of: 0.065 MnO; 0.272 Al.sub.2 O.sub.3 ; 0.262 P.sub.2 O.sub.5 ; 0.158 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.03R(Mn.sub.0.05 Al.sub.0.42 P.sub.0.41 Si.sub.0.12)O.sub.2
(h) The chemical analysis of MnAPSO-44 (Example 64D) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 25.8P.sub.2 O.sub.5 36.6MnO 4.4SiO.sub.2 9.7Carbon 2.5LOI* 23.1______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.062 MnO; 0.253 Al.sub.2 O.sub.3 ; 0.258 P.sub.2 O.sub.5 ; 0.161 SiO.sub.2 ;; and a formula (anhydrous basis) of:
0.04R(Mn.sub.0.05 Al.sub.0.41 P.sub.0.41 Si.sub.0.13)O.sub.2
(i) The chemical analysis of MnAPSO-47 (Example 49D) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 27.6P.sub.2 O.sub.5 36.2MnO 5.0SiO.sub.2 5.7Carbon 9.9LOI* 25.1______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.071 MnO; 0.271 Al.sub.2 O.sub.3 ; 0.255 P.sub.2 O.sub.5 ; 0.095 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.17R(Mn.sub.0.06 Al.sub.0.44 P.sub.0.42 Si.sub.0.08)O.sub.2
EXAMPLE 67D
EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on clear crystals from the products of certain examples, as identified in parenthesis hereinafter. Analysis of crystals having a morphology characteristic of each MnAPSO product gave the following analysis based on relative peak heights:
______________________________________ Average of Spot Probes______________________________________(a) MnAPSO-5 (Example 4D):Mn 0.5Al 8.0P 9.5Si 0.7(b) MnAPSO-11 (Example 24D):Mn 1.0Al 8.0P 9.5Si 1.5(c) MnAPSO-20 (Example 46D):Mn 0.8Al 8.2P 9.4Si 1.7(d) MnAPSO-34 (Example 6D):Mn 1.3Al 7.0P 9.0Si 1.5(e) MnAPSO-35 (Example 23D):Mn 1.0Al 7.0P 10.0Si 1.2(f) MnAPSO-36 (Example 59D):Mn 0.8Al 9.3P 9.9Si 1.6(g) MnAPSO-44 (Example 42D):Mn 0.7Al 9.0P 10.0Si 1.7(h) MnAPSO-44 (Example 64D):Mn 1.1Al 8.7P 10.0Si 5.6(i) MnAPSO-47 (Example 49D):Mn 1.0Al 9.0P 9.5Si 1.9______________________________________
EXAMPLE 68D
(a) The MnAPSO-5, prepared in Example 31D, was subjected to x-ray analysis. The MnAPSO-5 was impure but the major phase was determined to have an x-ray powder diffraction pattern characterized by the following data:
______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________ 6.9* 12.81 13 7.5 11.79 100 8.0* 11.05 5 9.1* 9.72 4 9.3* 9.51 413.0 6.81 14 13.7* 6.46 315.0 5.91 27 16.5* 5.37 3 18.5* 4.80 719.8 4.48 4321.0 4.23 5822.3 3.99 7524.7 3.60 625.9 3.440 4229.0 3.079 1830.0 2.979 3433.6 2.667 834.5 2.600 2136.9 2.436 437.7 2.386 1041.5 2.176 542.1 2.146 542.2 2.141 542.6 2.122 543.5 2.080 344.9 2.019 347.5 1.914 751.4 1.778 551.9 1.762 355.5 1.656 5______________________________________ *Peak may contain an impurity
(b) A portion of the as-synthesized MnAPSO-5 of part (a) was calcined in air at 500.degree. C. for about two (2) hours. The calcined product was characterized by the following x-ray powder diffraction pattern:
______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________ 7.4 11.95 100*7.8 11.33 412.9 6.86 2515.0 5.91 21*16.5 5.37 3*16.7 5.31 3*17.5 5.07 519.8 4.48 4021.2 4.19 4022.5 3.95 4326.0 3.427 3029.1 3.069 1130.1 2.969 3533.7 2.660 534.6 2.592 1937.1 2.423 437.9 2.374 642.5 2.127 443.1 2.099 346.0 1.973 347.9 1.899 555.8 1.647 4______________________________________ *Peak may contain an impurity
(c) The species denominated herein as MnAPSO-5 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empiracal chemical composition on an anhydrous basis expressed by the formula:
mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-5 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table V-D as follows:
TABLE V-D______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________7.3-7.7 12.11-11.48 vs14.7-15.1 6.03-5.87 m19.6-19.9 4.53-4.46 m20.8-21.3 4.27-4.17 m22.1-22.6 4.02-3.93 m29.8-30.2 2.998-2.959 m______________________________________
(d) All of the MnAPSO-5 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table VI-D below:
TABLE VI-D______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________7.3-7.7 12.11-11.48 10012.7-13.0 6.97-6.81 14-2714.7-15.1 6.03-5.87 20-6019.6- 19.9 4.53-4.46 36-5120.8-21.3 4.27-4.17 29-5822.1-22.6 4.02-3.93 30-7524.5-24.7 3.63-3.60 4-625.7-26.1 3.466-3.414 25-4228.8-29.2 3.100-3.058 10-3029.8-30.2 2.998-2.959 34-5033.4-33.8 2.683-2.652 4-1034.3-34.7 2.614-2.585 19-4436.7-37.2 2.449-2.417 3-437.5-38.0 2.398-2.368 5-2041.3-41.5 2.186-2.176 3-541.9-42.1 2.156-2.146 4-542.0-42.2 2.151-2.141 3-542.4-42.6 2.132-2.122 3-543.1-43.5 2.099-2.080 3-544.7-44.9 2.027-2.019 3-546.0-46.1 1.973-1.969 3-447.3-47.6 1.922-1.910 5-747.9-48.0 1.899-1.895 4-551.2-51.4 1.784-1.778 5-751.7-51.9 1.768-1.762 3-555.3-55.9 1.661-1.645 2-7______________________________________
EXAMPLE 69D
(a) MnAPSO-11, as prepared in example 24D, was subjected to x-ray analysis. The MnAPSO-11 was determined to have an x-ray powder diffraction pattern characterized by the following data:
______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________ 8.1 10.92 36 9.5 9.31 6113.1 6.76 1915.7 5.64 3616.2 5.47 1019.1 4.65 1320.5 4.33 4521.1 4.21 10022.2 4.00 5522.5 3.95 5222.7 3.92 6123.2 3.83 7124.5 3.63 1324.8 3.59 1625.0 3.562 1326.4 3.38 2628.3 3.153 1328.6 3.121 2329.5 3.028 1331.5 2.84 1632.8 2.730 2334.2 2.622 1635.4 2.54 1035.8 2.508 1036.3 2.475 1037.5 2.398 1337.8 2.370 1639.4 2.287 1042.9 2.108 1044.8 2.023 1048.8 1.866 350.6 1.804 1054.6 1.681 10______________________________________
(b) A portion of the as-synthesized MnAPSO-11 of part (a) was calcined in air at 600.degree. C. for about two (2) hours. The calcined product was characterized by the following x-ray powder diffraction pattern:
______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________ 8.1 10.92 33 9.8 9.03 6011.8 7.50 1312.8 6.92 2713.5 6.56 1314.8 5.99 sh16.1 5.51 6719.5 4.55 2719.9 4.46 4020.4 4.35 3321.5 4.13 7321.8 4.08 10022.2 4.00 7322.4 3.97 8023.5 3.79 7324.3 3.66 2725.8 3.453 3326.7 3.339 2727.3 3.267 3327.8 3.209 3328.5 3.132 2729.5 3.028 3329.8 2.998 4030.4 2.940 2731.8 2.814 2032.6 2.747 3334.0 2.637 2035.5 2.529 2737.1 2.423 2037.4 2.404 2038.2 2.356 2038.6 2.332 2741.0 2.201 20______________________________________
(c) The species denominated herein as MnAPSO-11 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-11 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VII-D as follows:
TABLE VII-D______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________9.4-9.8 9.41-9.03 m16.1-16.2 5.50-5.47 vw-m21.0-21.5 4.23-4.13 m-vs22.1-22.2 4.02-4.00 m22.4-22.5 3.97-3.95 m-s23.1-23.5 3.85-3.79 m______________________________________
(d) All of the MnAPSO-11 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table VIII-D below:
TABLE VIII-D______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________8.0-8.1 11.05-10.92 31-369.4-9.8 9.41-9.03 56-6111.8 7.50 1312.8-13.1 6.92-6.76 17-2713.5 6.56 1314.8 5.99 sh15.6-15.7 5.68-5.64 33-3616.1-16.2 5.50-5.47 8-6719.0-19.5 4.68-4.55 8-2719.9 4.46 4020.4-20.5 4.35-4.33 33-4521.0-21.5 4.23-4.13 73-10021.8 4.08 10022.1-22.2 4.02-4.00 55-7322.4-22.5 3.97-3.95 52-8022.6-22.7 3.93-3.92 6123.1-23.5 3.85-3.79 69-7324.3-24.5 3.66-3.63 11-2724.7-24.8 3.60-3.59 14-1624.9-25.0 3.58-3.562 sh-1325.8 3.453 3326.3-26.7 3.389-3.339 25-2727.3 3.267 3327.8 3.209 3328.2-28.3 3.164-3.153 11-1328.5-28.6 3.132-3.121 22-2729.4-29.5 3.038-3.028 11-3329.8 2.998 4030.4 2.940 2731.4-31.8 2.849-2.814 14-2032.6-32.8 2.747-2.730 19-3334.0-34.2 2.637-2.622 14-2035.3-35.5 2.543-2.529 sh-2735.7-35.8 2.515-2.508 8-1036.2-26.3 2.481-2.475 8-1037.1 2.423 2037.4-37.5 2.404-2.398 11-2037.7-37.8 2.386-2.380 16-1738.2 2.356 2038.6 2.332 2739.3-39.4 2.292-2.287 8-1041.0 2.201 2042.8-42.9 2.113-2.108 8-1044.7-44.8 2.027-2.023 8-1048.7-48.8 1.870-1.866 3-550.5-50.6 1.807-1.804 8-1054.5-54.6 1.684-1.681 8-10______________________________________
EXAMPLE 70D
(a) MnAPSO-16, as prepared in example 14D was subjected to x-ray analysis. The MnAPSO-16 was determined to have an x-ray powder diffraction pattern characterized by the following data:
______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________ 8.6* 10.28 811.0* 8.04 2311.4 7.76 4813.3* 6.66 1115.9* 5.57 517.3* 5.13 2417.7* 5.01 818.7 4.75 4021.1* 4.21 19 21.9** 4.06 10023.0 3.87 1323.2* 3.83 1023.7* 3.75 525.1 3.548 5 26.6** 3.351 2626.7* 3.339 (sh)27.8 3.209 528.8* 3.100 1529.0 3.079 1529.8 2.998 2432.0* 2.797 1632.6 2.747 7 34.7** 2.585 1035.7* 2.515 537.8 2.380 1139.7 2.270 542.0* 2.151 544.2 2.049 5 48.5** 1.877 1049.4* 1.845 552.4 1.746 554.7 1.678 5______________________________________ *Impurity Peak **Peak may contain impurity
(b) A portion of the as-synthesized MnAPSO-16 of part (a) was calcined in nitrogen at 600.degree. C. for about 2 hours. The calcined product was characterized by the following x-ray powder diffraction pattern:
______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________11.5 7.69 100 13.3* 6.66 918.6 4.77 25 20.3* 4.37 44 20.5* 4.33 41 21.5* 4.13 66 21.9** 4.06 7222.9 3.88 31 23.5* 3.79 13 26.5** 3.363 3127.9 3.198 1329.0 3.079 1929.7 3.008 3432.6 2.747 13 34.7** 2.585 13 35.6* 2.522 1637.8 2.380 13 48.2** 1.888 9______________________________________ *Impurity Peak **Peak may contain impurity
(c) The species denominated herein as MnAPSO-16 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-16 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table IX-D as follows:
TABLE IX-D______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________11.4-11.5 7.76-7.69 m-vs18.6-18.7 4.77-4.75 m21.9 4.06 m-vs22.9-23.0 3.88-3.87 w-m.sup.26.5-26.6 3.363-3.351 m29.7-29.8 3.008-2.998 m______________________________________
(d) All of the MnAPSO-16 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table X-D below:
TABLE X-D______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________11.4-11.5 7.76-7.69 48-10018.6-18.7 4.77-4.75 25-40 21.9* 4.06 72-8022.9-23.0 3.88-3.87 13-31 26.5-26.6* 3.363-3.351 26-3127.8-27.9 3.209-2.198 5-1329.0 3.079 15-1929.7-29.8 3.008-2.998 24-3432.6 2.747 7-14 34.7* 2.585 9-1437.8 2.380 11-1539.7 2.270 5-644.2 2.049 5-6 48.2-48.5* 1.888-1.877 9-1249.4 1.845 4-552.4 1.746 4-554.7 1.678 4-5______________________________________ *Peak might contain an impurity
EXAMPLE 71D
(a) MnAPSO-20, as prepared in example 46D was subjected to x-ray analysis. The MnAPSO-20 was determined to have an x-ray powder diffraction pattern characterized by the following data:
______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________14.0 6.35 4919.8 4.49 4322.1 4.02 3 23.7* 3.75 124.3 3.67 10028.1 3.177 1331.5 2.842 1134.6 2.595 1637.5 2.400 240.1 2.247 442.7 2.118 447.4 1.917 451.8 1.764 7______________________________________ *Peak may contain an impurity
(b) A portion of the as-synthesized MnAPSO-20 of part (a) was calcined in air at 500.degree. C. for about 1 hour. The calcined product was characterized by the following x-ray powder diffraction pattern:
______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________ 7.1 12.51 214.0 6.33 10019.8 4.48 4022.2 4.00 424.3 3.66 9928.2 3.168 1731.6 2.835 1534.7 2.589 1740.2 2.243 342.7 2.116 447.5 1.913 4______________________________________
(c) The species denominated herein as MnAPSO-20 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-20 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XI-D as follows:
TABLE XI-D______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________13.904-13.998 6.3692-6.3263 m-vs19.723-19.818 4.5011-4.4918 m24.223-24.329 3.6742-3.6584 vs28.039-28.163 3.1822-3.1684 w31.434-31.560 2.8458-2.8348 w34.527-34.652 2.5976-2.5866 w______________________________________
(d) All of the MnAPSO-20 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XII-D below:
TABLE XII-D______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________13.904-13.998 6.3692-6.3263 49-10019.723-19.818 4.5011-4.4918 40-4322.091-22.200 4.0236-4.0041 3-424.223-24.329 3.6742-3.6584 99-10028.039-28.163 3.1822-3.1684 13-1731.434-31.560 2.8458-2.8348 11-1534.527-34.652 2.5976-2.5886 15-1734.413-27.465 2.2501-2.4004 240.071-40.207 2.2501-2.2428 3-442.627-42.730 2.1209-2.1160 3-447.383-47.519 1.9185-1.9134 3-451.790-51.840 1.7652-1.7636 7______________________________________
EXAMPLE 72D
(a) MnAPSO-31, as prepared in example 54D was subjected to x-ray analysis. MnAPSO-31 was determined to have an x-ray powder diffraction pattern characterized by the following data:
______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________ 7.9 11.22 4 8.6 10.27 6117.2 5.17 518.5 4.81 420.4 4.36 4921.2 4.19 422.0 4.04 3022.1 4.02 3222.7 3.92 10025.3 3.526 525.8 3.459 328.1 3.181 1229.8 2.995 631.8 2.812 2235.2 2.548 936.2 2.482 337.3 2.411 337.8 2.382 338.3 2.353 338.4 2.346 339.4 2.285 339.8 2.266 340.3 2.241 346.8 1.942 348.8 1.866 251.8 1.766 555.6 1.654 2______________________________________
(b) A portion of the as-synthesized MnAPSO-31 of part (a) was calcined in air at 500.degree. C. for about 1.5 hours. The calcined product was characterized by the following x-ray powder diffraction pattern:
______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________ 8.6 10.31 5814.8 5.98 417.1 5.18 918.5 4.81 420.4 4.36 5222.1 4.03 4422.7 3.92 10025.3 3.526 725.8 3.460 828.1 3.181 1529.8 2.998 1131.1 2.879 331.8 2.811 3335.3 2.546 1136.3 2.477 637.3 2.409 337.8 2.383 338.3 2.348 339.4 2.289 440.3 2.236 345.4 2.000 346.8 1.942 547.6 1.909 448.9 1.864 351.7 1.767 6______________________________________
(c) The species denominated herein as MnAPSO-31 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-31 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIII-D as follows:
TABLE XIII-D______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________8.482-9.501 10.4240-9.3084 m20.222-20.353 4.3913-4.3632 m21.879-21.993 4.0622-4.0415 m22.071-22.088 4.0272-4.0242 m22.587-22.698 3.9364-3.9174 vs31.724-31.836 2.8546-2.8108 m______________________________________
(d) All of the MnAPSO-31 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XIV-D below:
TABLE XIV-D______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________7.694-7.883 11.4904-11.2145 2-48.482-9.501 10.4240-9.3084 58-6614.756-14.822 6.0034-5.9767 2-417.016-17.158 5.2105-5.1679 5-918.310-18.466 4.8451-4.8046 3-420.222-20.353 4.3913-4.3632 45-5221.032-21.221 4.2238-4.1867 4-521.879-21.993 4.0622-4.0415 30-5122.071-22.088 4.0272-4.0242 32-4422.587-22.698 3.9364-3.9174 10023.164-23.190 3.8398-3.8355 2-325.115-25-260 3.5457-3.5256 4-725.663-25.757 3.4712-3.4588 3-827.922-28.050 3.1953-3.1809 12-1529.701-29.831 3.0078-2.9950 6-1131.068-31.315 2.8785-2.8564 2-331.724-31.836 2.8564-2.8108 21-3335.117-35.251 2.5553-2.5460 9-1135.871 2.5033 136.070-36.261 2.4900-4730 2-637.123-37.325 2.4217-2.4091 2-337.628-27.763 2.3904-2.3822 2-338.163-38.254 2.3581-2.3527 2-338.334-38.367 2.3480-2.3461 339.285-39.442 2.2933-2.2845 3-439.654-39.772 2.2728-2.2663 2-440.111-40.337 2.2480-2.2359 2-345.179-45.354 2.0069-1.9996 2-346.617-46.786 1.9483-1.9416 3-547.454-47.631 1.9158-1.9091 2-448.610- 48.846 1.8729-1.8644 2-350.679-50.750 1.8012-1.7989 251.588-51.766 1.7716-1.7659 4-655.410-55.557 1.6581-1.6541 2______________________________________
EXAMPLE 73D
(a) MnAPSO-34, as prepared in example 11D was subjected to x-ray analysis. MnAPSO-34 was determined to have an x-ray powder diffraction pattern characterized by the following data:
______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________ 9.6 9.21 10012.9 6.86 1714.2 6.24 1516.1 5.51 3318.1 4.90 2320.6 4.31 6922.3 3.99 1023.1 3.85 825.2 3.534 2525.8 3.453 1927.5 3.243 1028.4 3.143 1029.5 3.028 1030.5 2.931 2731.2 2.867 2333.8 2.652 834.3 2.614 1236.3 2.475 843.0 2.103 643.5 2.080 647.5 1.914 648.9 1.863 850.9 1.794 653.0 1.728 655.7 1.650 6______________________________________
(b) A portion of the as-synthesized MnAPSO-34 of part (a) was calcined in nitrogen at 425.degree. C. for about 2 hours. The calcined product was characterized by the following x-ray powder diffraction pattern:
______________________________________2.theta. d, (.ANG.) I/Io .times. 100______________________________________ 9.6 9.21 10013.0 6.86 2514.1 6.28 516.2 5.47 1517.9 4.96 1519.1 4.65 520.8 4.27 3722.2 4.00 522.4 3.97 523.2 3.83 725.2 3.534 1526.0 3.427 1227.7 3.220 428.3 3.153 529.7 3.008 430.7 2.912 1731.3 2.849 1132.4 2.763 334.6 2.592 536.2 2.481 438.8 2.321 339.8 2.265 343.1 2.099 343.6 2.076 347.8 1.903 149.0 1.859 351.0 1.791 353.3 1.719 454.6 1.681 3______________________________________
(c) The species denominated herein as MnAPSO-34 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-34 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XV-D as follows:
TABLE XV-D______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________9.4-9.6 9.41-9.21 vs15.9-16.2 5.57-5.47 m20.4-20.8 4.35-4.27 m-vs25.0-25.3 3.562-3.520 w-m31.0-31.3 2.885-2.858 w-m33.6-33.9 2.667-2.644 m______________________________________
(d) All of the MnAPSO-34 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XIV-D below:
TABLE XIV-D______________________________________2.THETA. d, (.ANG.) I/Io .times. 100______________________________________9.4-9.6 9.41-9.21 10012.7-13.0 6.97-6.86 17-2514.0-14.2 6.33-6.24 5-1715.9-16.2 5.57-5.47 15-4417.9-18.1 4.96-4.90 15-3219.1 4.65 520.4-20.8 4.35-4.27 37-9222.1-22.3 4.02-3.99 5-1622.4 3.97 522.9-23.2 3.88-3.83 7-1625.0-25.3 3.562-3.520 15-3625.8-26.0 3.453-3.427 12-1927.3-27.7 3.267-3.220 4-2828.2-28.5 3.164-3.132 5-1629.3-29.7 3.048-3.008 4-1630.3-30.7 2.950-2.912 10-1731.0-31.3 2.885-2.849 11-4032.4 2.763 333.6-33.9 2.667-2.644 23-3234.3-34.6 2.614-2.592 5-1236.2-36.4 2.481-2.468 4-1638.8 2.321 339.8 2.265 343.0-43.1 2.103-2.099 3-1243.5-43.6 2.080-2.076 3-1247.4-47.8 1.918-1.903 1-1248.8-49.0 1.866-1.859 3-1250.8-51.0 1.797-1.791 3-1252.9-53.3 1.731-1.719 4-1254.6 1.681 355.6-55.8 1.653-1.647 6-12______________________________________
EXAMPLE 74D
(a) MnAPSO-35, as prepared in example 22D was subjected to x-ray analysis. MnAPSO-35 was determined to have an x-ray powder diffraction pattern characterized by the following data:
______________________________________2.THETA. d, (.ANG.) I/Io .times. 100______________________________________ 8.6 10.28 1410.9 8.12 4513.4 6.61 2315.9 5.57 1117.4 5.10 8017.8 4.98 1620.9 4.25 5721.9 4.06 10023.2 3.83 3424.8 3.59 925.7 3.466 726.9 3.314 2128.3 3.153 5029.1 3.069 1131.4 2.849 932.1 2.788 4134.3 2.614 1434.9 2.571 735.3 2.543 535.8 2.508 737.7 2.386 539.5 2.281 541.9 2.156 742.7 2.118 744.6 2.032 547.6 1.910 748.3 1.884 749.5 1.841 751.0 1.791 955.0 1.670 555.4 1.658 7______________________________________
(b) A portion of the as-synthesized MnAPSO-35 of part (a) was calcined in nitrogen at 500.degree. C. for about 2 hours. The calcined product was characterized by the following x-ray powder diffraction pattern:
______________________________________2.THETA. d, (.ANG.) I/Io .times. 100______________________________________8.6 10.28 2710.9 8.12 9611.4 7.76 1413.4 6.61 4115.8 5.61 1417.3 5.13 6817.7 5.01 sh20.8 4.27 6421.9 4.06 10023.3 3.82 3224.8 3.59 2325.7 3.466 1826.9 3.314 2728.3 3.153 5929.1 3.069 2331.4 2.849 1832.2 2.780 4634.2 2.622 1834.8 2.578 1435.8 2.508 941.9 2.156 942.5 2.127 944.6 2.032 947.4 1.918 948.2 1.888 949.4 1.845 951.0 1.791 1455.2 1.664 955.7 1.650 9______________________________________
(c) The species denominated herein as MnAPSO-35 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-35 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XVII-D as follows:
TABLE XVII-D______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________10.8-11.0 8.19-8.04 m-vs13.4-13.7 6.61-6.46 m-s17.2-17.5 5.16-5.07 m-s20.8-21.0 4.27-4.23 m21.8-22.3 4.08-3.99 m-vs28.2-28.7 3.164-3.110 m______________________________________
(d) All of the MnAPSO-35 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XVIII-D below:
TABLE XVIII-D______________________________________2.THETA. d, (.ANG.) I/Io .times. 100______________________________________8.5-8.7 10.40-10.16 13-3110.8-11.0 8.19-8.04 44-10011.4-11.5 7.76-7.69 8-1413.3-13.4 6.66-6.61 22-4113.4-13.7 6.61-6.46 31-8115.8-15.9 5.61-5.57 10-1417.2-17.5 5.16-5.07 38-8217.7-18.0 5.01-4.93 (sh)-1820.8-21.0 4.27-4.23 44-4621.8-22.3 4.08-3.99 56-10023.1-23.6 3.85-3.77 31-3424.7-25.2 3.60-3.534 13-3125.6-25.8 3.480-3.453 4-2526.8-27.4 3.326-3.255 19-4428.2-28.7 3.164-3.110 50-5929.0-29.6 3.079-3.018 10-3131.3-31.4 2.858-2.849 9-1832.0-32.8 2.797-2.730 31-4634.2-34.3 2.622-2.614 11-1834.8-34.9 2.578-2.571 4-1435.2-35.3 2.550-2.543 5-735.7-35.8 2.515-2.508 4-937.6-37.7 2.392-2.386 4-539.4-39.5 2.287-2.281 4-741.8-42.0 2.161-2.151 6-942.5-42.8 2.127-2.113 5-944.5-44.7 2.036-2.027 5-947.4-47.7 1.918-1.907 6-948.2-48.4 1.888-1.881 6-949.4-49.6 1.845-1.838 6-950.9-51.1 1.794-1.787 5-1454.9-55.2 1.672-1.664 5-955.3-55.7 1.661-1.650 6-9______________________________________
EXAMPLE 75D
(a) MnAPSO-36, as prepared in example 59D was subjected to x-ray analysis. The MnAPSO-36 was determined to have an x-ray powder diffraction pattern characterized by the following data:
______________________________________2.THETA. d, (.ANG.) I/Io .times. 100______________________________________7.4 11.88 157.9 11.22 1008.2 10.82 3313.5 6.55 515.8 5.61 1016.4 5.41 3119.1 4.66 1420.7 4.28 3421.2 4.19 421.7 4.10 1622.0 4.04 1422.5 3.96 1523.0 3.87 523.9 3.73 627.2 3.276 1527.9 3.193 328.3 3.153 829.0 3.079 730.2 2.958 430.3 2.951 432.0 2.798 834.8 2.579 7______________________________________
(b) A portion of the as-synthesized MnAPSO-36 of part (a) was calcined in air at 500.degree. C. for about 1 hour. The calcined product was characterized by the following x-ray powder diffraction pattern:
______________________________________2.THETA. d, (.ANG.) I/Io .times. 100______________________________________7.1 12.39 57.6 11.64 218.0 11.11 1008.3 10.65 3713.6 6.53 1716.6 5.35 3119.4 4.57 1720.8 4.27 1921.9 4.06 822.4 3.97 1522.7 3.92 1123.4 3.80 523.9 3.73 727.3 3.271 1628.3 3.159 628.4 3.141 629.1 3.074 729.4 3.043 532.0 2.798 6______________________________________
(c) The species denominated herein as MnAPSO-36 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-36 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIX-D as follows:
TABLE XIX-D______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________7.596 11.6382 m7.628-7.981 11.5899-11.0771 vs8.105-8.299 10.9084-10.6537 m16.395-16.673 5.4066-5.3172 m19.052-19.414 4.6580-4.5721 w20.744-20.871 4.2819-4.2560 m______________________________________
(d) All of the MnAPSO-36 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XX-D below:
TABLE XX-D______________________________________2.THETA. d, (.ANG.) I/Io .times. 100______________________________________7.132 12.3939 57.596 11.6382 217.628-7.981 11.5899-11.0771 1008.105-8.299 10.9084-10.6537 33-3713.517-13.778 6.5503-6.4270 5-1715.797-15.928 5.6099-5.5640 10-1116.395-16.673 5.4066-5.3172 31-3219.052-19.414 4.6580-4.5721 14-1720.744-20.871 4.2819-4.2560 20-3521.230 4.1848 421.655 4.1037 1621.863-21.986 4.0651-4.0427 8-1422.119-22.470 4.0186-3.9566 1522.713-23.408 3.9150-3.8001 5-1123.854-23.965 3.7301-3.7131 5-627.219-27.518 3.2761-3.2412 15-1627.868-27.939 3.2014-3.1934 2-328.252 3.1587 628.304-28.536 3.1530-3.1279 6-829.003-29.268 3.0786-3.0513 6-729.347 3.0433 530.144-30.230 2.9646-2.9564 430.291-30.526 2.9505-2.9284 431.983-32.094 2.7982-2.7888 6-934.640-34.968 2.5894-2.5659 7______________________________________
EXAMPLE 76D
(a) MnAPSO-44, as prepared in example 64D was subjected to x-ray analysis. The MnAPSO-44 was determined to have an x-ray powder diffraction pattern characterized by the following data:
______________________________________2.THETA. d, (.ANG.) I/Io .times. 100______________________________________9.4 9.39 10013.0 6.83 2013.7 6.45 416.1 5.52 4317.3 5.12 519.0 4.68 720.7 4.29 8421.7 4.09 2122.6 3.94 823.1 3.86 924.4 3.65 5826.1 3.409 2227.8 3.205 1029.7 3.012 530.1 2.969 1630.8 2.900 5032.5 2.753 432.9 2.721 634.8 2.577 335.5 2.528 938.5 2.336 239.2 2.299 240.0 2.255 242.2 2.143 342.5 2.125 343.6 2.076 247.3 1.922 248.2 1.890 748.7 1.870 450.3 1.814 753.9 1.701 6______________________________________
(b) A portion of the as-synthesized MnAPSO-44 of part (a) was calcined in air at 500.degree. C. for about one (1) hour. The calcined product was characterized by the following x-ray powder diffraction pattern:
______________________________________2.THETA. d, (.ANG.) I/Io .times. 100______________________________________9.6 9.21 10013.1 6.79 2614.2 6.26 316.2 5.46 1218.0 4.93 1819.3 4.60 320.9 4.25 2822.3 3.99 323.4 3.80 325.3 3.526 1326.3 3.387 928.5 3.137 328.6 3.123 429.9 2.990 230.0 2.976 230.6 2.921 331.1 2.875 731.8 2.811 232.1 2.791 235.1 2.560 3______________________________________
(c) The species denominated herein as MnAPSO-44 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being with the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-44 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXI-D as follows:
TABLE XXI-D______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________9.420-9.498 9.3883-9.3110 vs16.062-16.131 5.5179-5.4944 m20.715-20.790 4.2877-4.2725 s24.396-24.424 3.6485-3.6444 m26.143-26.184 3.4085-3.4032 m30.833-30.853 2.8999-2.8981 m______________________________________
(d) All of the MnAPSO-44 compositions, both as-synthesized and calcined, for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XXII-D below:
TABLE XXII-D______________________________________2.THETA. d, (.ANG.) I/Io .times. 100______________________________________9.420-9.498 9.3883-9.3110 10012.930-12.958 6.8468-6.8318 2013.738 6.4458 416.062-16.131 5.5179-5.4944 4317.329-17.396 5.1173-5.0975 518.950-18.998 4.6828-4.6713 720.715-20.790 4.2877-4.2725 8421.709-21.743 4.0937-4.0873 2122.366-22.583 3.9748-3.9372 823.061-23.101 3.8566-3.8501 924.396-24.424 3.6485-3.6444 5826.143-26.184 3.4085-3.4032 2227.837-27.881 3.2049-3.1999 1029.661 3.0117 530.002-30.096 2.9783-2.9692 1630.833-20.853 2.8999-2.8981 5032.520-32.562 2.7532-2.7498 432.900-32.918 2.7223-2.7208 634.812 2.5770 335.516-35.534 2.5275-2.5263 938.536 2.3361 238.185 2.2989 239.991 2.2545 242.162-42.177 2.1432-2.1425 342.533-42.541 2.1254-2.1250 343.607-73.621 2.0755-2.0749 247.283 1.9224 248.157-48.177 1.8895-1.8888 748.640-48.697 1.8719-1.8698 450.303-50.307 1.8138-1.8137 753.885-53.887 1.7014-1.7013 6______________________________________
EXAMPLE 77D
(a) MnAPSO-47, as prepared in example 49D was subjected to x-ray analysis. The MnAPSO-47 was determined to have an x-ray powder diffraction pattern characterized by the following data:
______________________________________2.THETA. d, (.ANG.) I/Io .times. 100______________________________________4.8 18.44 19.4 9.38 10012.9 6.89 513.9 6.40 316.0 5.56 917.5 5.06 418.9 4.69 320.5 4.32 3021.8 4.08 422.4 3.98 122.9 3.88 324.6 3.61 1125.9 3.445 727.6 3.234 227.9 3.199 129.5 3.033 230.5 2.930 1030.8 2.901 731.5 2.845 133.2 2.700 134.4 2.604 234.8 2.576 135.7 2.516 238.4 2.343 139.2 2.297 139.6 2.277 142.4 2.132 143.3 2.091 147.6 1.911 148.6 1.874 550.3 1.813 253.2 1.722 154.0 1.698 1______________________________________
(b) A portion of the as-synthesized MnAPSO-47 of part (a) was calcined in air at 500.degree. C. for about one (1) hour. The calcined product was characterized by the following x-ray powder diffraction pattern:
______________________________________2.THETA. d, (.ANG.) I/Io .times. 100______________________________________5.0 17.80 19.7 9.12 10010.0 8.85 113.1 6.75 514.2 6.23 116.3 5.45 218.0 4.92 219.4 4.58 320.9 4.24 722.4 3.98 123.4 3.80 125.3 3.521 226.3 3.385 228.1 3.176 128.6 3.125 130.0 2.977 131.1 2.876 331.5 2.837 233.9 2.645 135.0 2.562 149.6 1.838 1______________________________________
(c) The species denominated herein as MnAPSO-47 is a molecular sieve having a three dimensional microporous crystalline framework structure of MnO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Mn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of manganese, aluminum, phosphorus and silicon respectively, present as tetrahedral oxide, said mole fractions being within the pentagonal compostional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compostional area defined by points a, b, c and d of FIG. 2, said MnAPSO-47 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXIII-D as follows:
TABLE XXIII-D______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________9.434-9.696 9.3746-9.1214 vs15.946-16.276 5.5579-5.4457 vw20.539-20.940 4.3242-4.2423 vw-m24.643 3.6125 w30.511 2.9297 w30.820-31.096 2.9011-2.8759 vw______________________________________
(d) All of the MnAPSO-47 compositions, both as-synthesized and calcined for which x-ray power diffraction data have presently been obtain have patterns which are within the generalized pattern of Table XXIV-D below:
TABLE XXIV-D______________________________________2.THETA. d, (.ANG.) I/Io .times. 100______________________________________4.793-4.964 18.4368-17.8028 19.434-9.696 9.3746-9.1214 10012.847-13.107 6.8907-6.7543 513.840-14.211 6.3983-6.2321 1-315.946-16.276 5.5579-5.4457 2-917.544-18.032 5.0550-4.9191 2-418.941-19.365 4.6851-4.5836 320.539-20.940 4.3242-4.2423 6-3021.811 4.0747 422.351-22.352 3.9775-3.9774 122.936 3.8773 323.401 3.8013 124.643 3.6125 1125.294-25.864 3.5210 2-726.327-27.577 3.3851-3.2344 227.881-28.093 3.1992-3.1762 128.560 3.1253 129.448-30.019 3.0331-2.9767 1-230.511 2.9297 1030.820-31.096 2.9011-2.8759 3-731.448-31.532 2.8446-2.8372 1-233.186-33.894 2.6995-2.6447 134.444 2.6037 234.834-35.026 2.5755-2.5618 135.685 2.5159 238.412 2.3434 139.223 2.2968 139.582 2.2768 142.403 2.1316 143.278 2.0905 147.595 1.9105 148.584-49.595 1.8739-1.8380 1-550.327 1.8130 253.205 1.7215 154.006 1.6979 1______________________________________
EXAMPLE 78D
The catalytic activity of MnAPSO compositions, calcined samples of the MnAPSO products of Examples 11D, 21D, 25D, 31D, 49D, 55D, 59D and 64D were tested for catalytic cracking.
The catalytic activity was determined using a reactor comprising a cylindrical quartz tube 254 mm. in length and 10.3 mm. I.D. In each test MnAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. Most of the MnAPSO samples had been previously calcined in air or nitrogen to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500.degree. C. for one hour. The feedstock was a helium- n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.
The pseudo-first-order rate constant (k.sub.A) was calculated to determine the relative catalytic activity of the MnAPSO compositions. The k.sub.A value (cm.sup.3 /g min) obtained for the MnAPSO compositions are set forth, below, in Table XXV-D:
TABLE XXV-D______________________________________ Prepared in RateMnAPSO Example No.: Constant (k.sub.A)*______________________________________MnAPSO-5 31D 0.2MnAPSO-11 25D 0.6MnAPSO-20 46D 0.2MnAPSO-31 55D 1.0; 0.5MnAPSO-34 11D 3.1MnAPSO-35 21D 0.1**MnAPSO-36 59D 0.3MnAPSO-44 64D 1.5MnAPSO-47 49D 1.7______________________________________ *Prior to determination of the catalystic activity of a given MnAPSO, eac was calcined as follows: (a)MnAPSO5 was calcined at 500.degree. C. in air for 2 hours; (b)MnAPSO11, MnAPSO34 and MnAPSO36 were calcined in situ; (c)MnAPSO31 was calcined in air at 500.degree. C. for 1.5 hours and then at 600.degree. C. for 1 hours; (d)MnAPSO35 was calcined at 500.degree. C. in nitrogen for 1 hour; and (e)MnAPSO20, MnAPSO44 and MnAPSO47 were calcined at 500.degree. C. in air for 1 hour. **Less than 0.1
TITANIUM-ALUMINUM-PHOSPHORUS-SILICON-OXIDE SIEVES
Molecular sieves containing titanium, aluminum, phosphorus and silicon as framework tetrahedral oxides are prepared as follows:
PREPARATIVE REAGENTS
In the following examples the TiAPSO compositions were prepared using numerous regents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:
(a) Alipro: aluminum isopropoxide;
(b) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO.sub.2 and 0.1 weight percent Na.sub.2 O;
(c) H.sub.3 PO.sub.4 : 85 weight percent aqueous phosphoric acid;
(d) Tiipro: titanium isopropoxide;
(e) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(f) Pr.sub.2 NH: di-n-propylamine, (C.sub.3 H.sub.7).sub.2 NH.
(g) Pr.sub.3 NH: tri-n-propylamine, (C.sub.3 H.sub.7).sub.3 N;
(h) Quin: Quinuclidine, (C.sub.7 H.sub.13 N);
(i) MQuin: Methyl Quinuclidine hydroxide, (C.sub.7 H.sub.13 NCH.sub.3 OH); and
(j) C-hex: cyclohexylamine.
PREPARATIVE PROCEDURES
The following preparative examples were carried out by forming a starting reaction mixture by adding the H.sub.3 PO.sub.4 and the water. This mixture was mixed and to this mixture the aluminum isoproxide was added. This mixture was then blended until a homogeneous mixture was observed. To this mixture the LUDOX-LS was added and the resulting mixture blended (about 2 minutes) until a homogeneous mixture was observed.
The titanium isopropoxide was added to the above mixture and the resulting mixture blended until a homogeneous mixture was observed. The organic templating agent was then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture was observed, i.e., about 2 to 4 minutes. When the organic templating agent was quinuclidine the procedure was modified such that the quinuclidine was dissolved in about one half the water and accordingly the H.sub.3 PO.sub.4 was mixed with about one half the water. (The pH of the mixture was measured and adjusted for temperature). The mixture was than placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150.degree. C. or 200.degree. C.) for a time or placed in lined screw top bottles for digestion at 100.degree. C. All digestions were carried out at the autogeneous pressure.
The molar composition for each preparation will be given by the relative moles of the components of the reaction mixture. H.sub.3 PO.sub.4 and titanium isopropoxide are given respectively in terms of the P.sub.2 O.sub.5 and TiO.sub.2 content of the reaction mixture.
All digestions were carried out at the autogeneous pressure. The products were removed from the reaction vessel cooled and evaluated as set forth hereinafter.
EXAMPLES 1E TO 30E
TiAPSO molecular sieves were prepared according to the above described preparative procedure and the TiAPSO products determined by x-ray analysis. The results of examples 1E to 30E are set forth in Tables I-E and II-E.
TABLE I-E______________________________________ Temp TimeExample Template.sup.1 (.degree.C.) (days) TiAPSO Product(s).sup.2______________________________________1E Quin 150 28 TiAPSO-162E Quin 200 10 TiAPSO-35; TiAPSO-163E Quin 200 28 TiAPSO-35; TiAPSO-164E Quin 225 5 TiAPSO-165E Pr.sub.3 N 150 3 TiAPSO-56E Pr.sub.3 N 150 11 TiAPSO-57E Pr.sub.3 N 200 3 TiAPSO-58E Pr.sub.3 N 200 11 TiAPSO-59E Pr.sub.3 N 100 3 --10E Pr.sub.3 N 100 11 --______________________________________ .sup.1 Reaction mixture comprised: 1.0 R: 0.2 TiO.sub.2 : 0.9 Al.sub.2 O.sub.3 : 0.9 P.sub.2 O.sub.5 : 0.2 SiO.sub.2 : 50 H.sub.2 O where "R" is the organic template. .sup.2 Major species as identified by xray powder diffraction pattern of product, except that when two or more species were identified the species are listed in the order of their predomenance in the product. The "--"denotes that TiAPSO products were not identified by Xray analysis.
TABLE II-E______________________________________ Temp TimeExample Template.sup.1 (.degree.C.) (days) TiAPSO Product(s).sup.2______________________________________11E C-hex 225 5 TiAPSO-44; TiAPSO-3512E Pr.sub.2 NH 150 4 TiAPSO-11; TiAPSO-4113E Pr.sub.2 NH 150 11 TiAPSO-1114E Pr.sub.2 NH 200 4 TiAPSO-1115E Pr.sub.2 NH 200 11 TiAPSO-1116E Pr.sub.2 NH 100 4 --17E Pr.sub.2 NH 100 11 --18E TEAOH 150 4 TiAPSO-34; TiAPSO-519E TEAOH 150 10 TiAPSO-34; TiAPSO-520E TEAOH 200 4 TiAPSO-5; TiAPSO-3421E TEAOH 200 10 TiAPSO-5; TiAPSO-3422E TEAOH 100 17 --23E TEAOH 150 2 TiAPSO-34; TiAPSO-524E TEAOH 150 13 TiAPSO-3425E TEAOH 200 2 TiAPSO-34; TiAPSO-526E TEAOH 200 13 TiAPSO-3427E MQuin 150 21 --28E MQuin 200 21 TiAPSO-3529E MQuin 150 45 TiAPSO-3530E MQuin 200 45 TiAPSO-35______________________________________ .sup.1 The reaction mixture generally comprised: kR: 0.2 TiO.sub.2 : 0.9 Al.sub.2 O.sub.3 : p P.sub.2 O.sub.5 : q SiO.sub.2 : 50 H.sub.2 O where R is the organic template; "k" is 1.0 for examples 11E to 22E and 27E to 30 and is 1.5 for examples 23E to 26E; "p" is 0.9 for examples 12E-30E and i 1.0 for example 11E; and "q" is 0.6 for examples 11E and 23E-26E and is 0.2 for examples 12E-22E and 27E-30E. .sup.2 Major species as identified by xray powder diffraction pattern of product, except that when two or more species were identified the species are listed in the order of their predomenance in the product. The "--" denotes that TiAPSO products were not identified by Xray analysis.
EXAMPLE 31E
Samples of the products of examples 4E, 6E, 15E, 24E and 30E were subjected to chemical analysis. The chemical analysis for each product is given hereinafter with the example in which the TiAPSO was prepared being given in parenthesis after the designation of the TiAPSO species.
(a) The chemical analysis for TiAPSO-16 (Example 4E) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 27.1P.sub.2 O.sub.5 36.1TiO.sub.2 6.8SiO.sub.2 6.7Carbon 12.0Nitrogen 1.9LOI* 22.9______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.085 TiO.sub.2 : 0.266 Al.sub.2 O.sub.3 : 0.254 P.sub.2 O.sub.5 : 0.112 SiO.sub.2 : and a formula (anhydrous basis) of:
0.14R(Ti.sub.0.07 Al.sub.0.43 P.sub.0.41 Si.sub.0.09)O.sub.2
(b) The chemical analysis for TiAPSO-35 (Example 30E) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 23.4P.sub.2 O.sub.5 28.3TiO.sub.2 17.6SiO.sub.2 4.37Carbon 11.3Nitrogen 1.6LOI* 26.3______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.220 TiO.sub.2 : 0.230 Al.sub.2 O.sub.3 : 0.199 P.sub.2 O.sub.5 : 0.073 SiO.sub.2 : and a formula (anhydrous basis) of:
0.12R(Ti.sub.0.19 Al.sub.0.40 P.sub.0.35 Si.sub.0.06)O.sub.2
(c) The chemical analysis for TiAPSO-5 (Example 6E) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 34.0P.sub.2 O.sub.5 46.9TiO.sub.2 3.0SiO.sub.2 1.2Carbon 5.8Nitrogen 0.74LOI* 14.4______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.038 TiO.sub.2 : 0.334 Al.sub.2 O.sub.3 : 0.330 P.sub.2 O.sub.5 : 0.020 SiO.sub.2 : and a formula (anhydrous basis) of:
0.054R(Ti.sub.0.03 Al.sub.0.48 P.sub.0.48 Si.sub.0.01)O.sub.2
(d) The chemical analysis of TiAPSO-11 (Example 15E) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 35.8P.sub.2 O.sub.5 49.0TiO.sub.2 1.08SiO.sub.2 3.3Carbon 5.0Nitrogen 1.0LOI* 10.5______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.014 TiO.sub.2 : 0.351 Al.sub.2 O.sub.3 : 0.345 P.sub.2 O.sub.5 : 0.055 SiO.sub.2 : and a formula (anhydrous basis) of:
0.07R(Ti.sub.0.01 Al.sub.0.48 P.sub.0.47 Si.sub.0.04)O.sub.2
(e) The chemical analysis for TiAPSO-34 (example 24E) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 32.3P.sub.2 O.sub.5 37.9TiO.sub.2 0.4SiO.sub.2 8.2Carbon 9.8Nitrogen 1.6LOI* 20.5______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.01 TiO.sub.2 : 0.32 Al.sub.2 O.sub.3 : 0.27 P.sub.2 O.sub.5 : 0.14 SiO.sub.2 : and a formula (anhydrous basis) of:
0.103R(Ti.sub.0.01 Al.sub.0.48 P.sub.0.41 Si.sub.0.11)O.sub.2
EXAMPLE 32E
EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope was carried out on clear crystals from the products of example 4E, 11E, 12E, and 21E. Analysis of crystals having a morphology characteristic of TiAPSO compositions gave the following analysis based on relative peak heights:
(a) TiAPSO-44/35 (Example 11E):
______________________________________ Average of Spot Probes______________________________________Ti 0.02Al 0.97P 0.94Si 0.25______________________________________
(b) TiAPSO-16 (Example 4E):
______________________________________ Average of Spot Probes______________________________________Ti 0.38Al 0.79P 0.84Si 0.33______________________________________
(c) TiAPSO-34/5 (Example 21E):
______________________________________ Average of Spot Probes______________________________________Ti 0.005Al 0.85P 1.00Si 0.08______________________________________
(d) TiAPSO-11 (Example 12E):
______________________________________ Average of Spot Probes______________________________________Ti 0.12Al 0.88P 0.84Si 0.07______________________________________
EXAMPLE 33E
Samples of the TiAPSO products of examples 4E, 13E, and 6E were evaluated for adsorption capacities in the calcined form by calcination in air to remove at least part of the organic templating agent, as hereinafter set forth. The adsorption capacities of each calcined sample were measured using a standard McBain- Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum at 350.degree. C. prior to measurement. The McBain-Bakr data for the aforementioned calcined TiAPSO products were:
(a) TiAPSO-16 (Example 4E):
______________________________________ Kinetic Pressure Temp Wt. %*Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed______________________________________O.sub.2 3.46 102 -183 3.3O.sub.2 3.46 744 -183 12.8**n-hexane 4.3 95 23.6 7.0H.sub.2 O 2.65 4.6 23.3 13.4H.sub.2 O 2.65 19 23.2 25.4______________________________________ *TiAPSO-16 was calcined at 500.degree. C. in air for 1.5 hours prior to being activated. **Sample may not have been fully equilibrated.
The above data demonstrate that the pore size of the calcined product is about 4.3 .ANG..
(b) TiAPSO-11 (Example 13E):
______________________________________ Kinetic Pressure Temp Wt. %*Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed______________________________________O.sub.2 3.46 101 -183 9.3O.sub.2 3.46 736 -183 10.3neopentane 5.0 742 23.0 1.1cyclohexane 6.0 67 22.9 5.2H.sub.2 O 2.65 4.6 22.4 12.4H.sub.2 O 2.65 19 22.5 23.4______________________________________ *TiAPSO-11 was calcined at 600.degree. C. in air for 1.5 hours prior to being activated.
The above data demonstrate that the pore size of the calcined product is about 6.0.ANG..
(c) TiAPSO-5 (Example 6E):
______________________________________ Kinetic Pressure Temp Wt. %*Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed______________________________________O.sub.2 3.46 101 -183 13.0O.sub.2 3.46 736 -183 14.5neopentane 6.2 742 23.0 4.9cyclohexane 6.0 67 22.9 7.1H.sub.2 O 2.65 4.6 22.4 14.7H.sub.2 O 2.65 19 22.5 23.4______________________________________ *TiAPSO was calcined at 600.degree. C. in air for 2.5 hours prior to bein activated.
The above data demonstrate that the pore size of the calcined product is greater than 6.2.ANG..
EXAMPLE 34E
(a) TiAPSO-5 compositions, as referred to herein in both the as-synthesized and calcined forms, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table III below:
TABLE III-E______________________________________2.theta. d, .ANG. Relative Intensity______________________________________7.3-7.5 12.11-11.79 s-vs19.7-19.9 4.51-4.46 m20.9-21.0 4.25-4.23 m-s22.3-22.5 3.99-3.95 m-vs25.8-26.1 3.453-3.411 m28.9-29.1 3.089-3.069 w-m______________________________________
(b) TiAPSO-5 compositions for which x-ray powder diffraction data have been obtained to data have patterns which are X-ray powder diffraction patterns characterized by Table IV-E below.
TABLE IV-E______________________________________2.theta. d,(.ANG.) 100 .times. I/Io______________________________________7.3-7.5 12.11-11.79 94-10012.9-13.0 6.86-6.81 19-2214.9-15.0 5.95-5.91 9-2119.7-19.9 4.51-4.46 26-5020.9-21.0 4.25-4.23 43-8222.3-2.5 3.99-3.95 60-10024.6-24.8 3.62-3.59 7-925.8-26.1 3.453-3.414 25-4028.9-29.1 3.089-3.069 17-2730.0-30.2 2.979-2.959 18-2533.5-33.7 2.675-2.660 6-934.5-34.7 2.600-2.585 17-1936.8-37.1 2.442-2.423 637.5-37.8 2.398-2.380 10-1341.4-41.5 2.181-2.176 5-641.7-42.0 2.166-2.151 3-442.5-42.9 2.127-2.108 3-643.6-43.7 2.076-2.071 3--444.9-45.0 2.019-2.014 3--447.4-47.6 1.918-1.910 5-747.8-47.9 1.903-1.900 6-751.4-51.5 1.778-1.774 4-551.8-51.9 1.765-1.762 3-455.6 1.653 6______________________________________
(c) A portion of the as-synthesized TiAPSO-5 of Example 6E was subjected to X-ray analysis. The TiAPSO-5 product was characterized by the x-ray powder diffraction pattern of Table V-E, below:
TABLE V-E______________________________________2.theta. d,(.ANG.) 100 .times. I/Io______________________________________7.3 12.11 949.1* 9.72 312.9 6.86 1913.6* 6.51 614.9 5.95 2118.2* 4.87 619.7 4.51 5020.9 4.25 8222.3 3.99 10024.6 3.62 925.8 3.453 4028.9 3.089 2730.0 2.979 2533.5 2.675 934.5 2.600 1936.8 2.442 637.5 2.398 1341.4 2.181 642.0 2.151 442.5 2.127 643.6 2.076 444.9 2.019 347.6 1.910 751.4 1.778 451.8 1.765 455.6 1.653 6______________________________________ *peak may contain an impurity.
(d) The TiAPSO-5 compositions of Example 6E was calcined at 600.degree. C. in air for 2.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern shown in Table VI-E, below:
TABLE VI-E______________________________________2.theta. d,(.ANG.) 100 .times. I/Io______________________________________7.5 11.79 10012.5* 7.08 813.0 6.81 2215.0 5.91 919.9 4.46 2621.0 4.23 4322.5 3.95 6024.8 3.59 726.1 3.414 2529.1 3.069 1730.2 2.959 1833.7 2.660 634.7 2.585 1737.1 2.423 637.8 2.380 1041.7 2.166 342.9 2.108 347.4 1.918 547.9 1.900 651.4 1.778 351.8 1.765 3______________________________________ *peak may contain an impurity.
EXAMPLE 35-E
(a) TiAPSO-11, as referred to herein in both the as-synthesized and calcined forms, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VII-E below:
TABLE VII-E______________________________________2.theta. d,(.ANG.) Relative Intensity______________________________________9.4-9.6 9.41-9.21 vw-m19.9-20.5 4.46-4.33 m21.0-21.8 4.23-4.08 vs22.0-22.1 4.04-4.02 m-vs22.4-22.6 3.97-3.93 m-s22.7 3.92 m23.1-23.4 3.85-3.80 m-vs______________________________________
(b) The TiAPSO-11 compositions for which x-ray powder diffraction data have been obtained to data have patterns which are characterized by the x-ray powder diffraction pattern of Table VIII-E below:
TABLE VIII-E______________________________________2.theta. d,(.ANG.) 100 .times. I/Io______________________________________8.0-8.1 11.05-10.92 23-599.4-9.6 9.41-9.21 sh-73 9.8 9.03 5112.8-13.2 6.92-6.71 26-2713.5-13.7 6.56-6.46 9-1114.7-15.0 6.03-5.91 9-1815.6-16.1 5.68-5.51 32-6316.2-16.3 5.47-5.44 7-1819.0-19.5 4.67-4.55 20-2319.9-20.5 4.46-4.33 31-6821.0-21.8 4.23-4.08 10022.0-22.1 4.04-4.02 57-10022.4-22.6 3.97-3.93 54-8222.7 3.92 7323.1-23.4 3.85-3.80 63-9123.9-24.4 3.72-3.65 2324.7 3.60 2726.5-26.6 3.363-3.351 17-3627.2-27.3 3.278-3.267 16-2027.6-27.7 3.232-3.220 20-2327.8-27.9 3.209-3.200 20-2128.5-28.6 3.132-3.121 14-2728.7 3.110 11-3229.0-29.5 3.079-3.028 27-3129.6-29.7 3.018-3.008 23-3430.3-30.4 2.950-2.940 20-2231.4-31.6 2.849-2.831 14-2332.5-32.9 2.755-2.722 26-3233.9-34.2 2.644-2.622 11-2335.5-35.6 2.529-2.522 17-1936.5 2.462 1837.2-37.5 2.417- 2.398 14-2338.7-39.4 2.327-2.287 14-1741.0 2.201 1142.8 2.113 1443.6 2.076 944.5-44.6 2.036-2.032 9-1445.0 2.014 1448.7-49.2 1.870-18.52 1449.4 1.845 1149.6 1.838 1150.6 1.804 7-1853.4 1.716 1153.6 1.707 954.6-54.7 1.681-1.678 9-1455.4-55.8 1.658-1.647 11-14______________________________________
(c) A portion of the as-synthesized TiAPSO-11 of Example 13E was subjected to x-ray analysis. The TiAPSO-11 product was characterized by the x-ray powder diffraction pattern of Table IX-E, below:
TABLE IX-E______________________________________2.theta. d,(.ANG.) 100 .times. I/Io______________________________________8.1 10.92 599.4 9.41 7313.2 6.71 2715.0 5.91 1815.7 5.64 5016.3 5.44 1819.0 4.67 2320.5 4.33 6821.0 4.23 10022.1 4.02 7322.6 3.93 8222.7 3.92 7323.2 3.83 9124.4 3.65 2324.7 3.60 2726.5 3.363 3628.5 3.132 2728.7 3.110 3229.0 3.079 2729.5 3.028 2331.4 2.849 2332.9 2.722 3234.2 2.622 2336.5 2.462 1837.5 2.398 2339.4 2.287 1442.8 2.113 1444.6 2.032 1445.0 2.014 1448.7 1.870 1450.6 1.804 1854.7 1.678 1455.4 1.658 14______________________________________
(d) The TiAPSO-11 composition of Example 13E was calcined at 500.degree. C. in air for 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern shown in Table X-E, below:
TABLE X-E______________________________________2.theta. d,(.ANG.) 100 .times. I/Io______________________________________8.1 10.92 239.6 9.21 sh9.8 9.03 5112.8 6.92 2613.5 6.56 1113.7 6.46 914.7 6.03 916.1 5.51 6319.5 4.55 2019.9 4.46 3121.8 4.08 10022.1 4.02 5722.4 3.97 5423.4 3.80 6323.9 3.72 2324.2 3.68 1726.6 3.351 1727.2 3.278 2027.6 3.232 2327.8 3.209 2028.5 3.132 1428.7 3.110 1129.5 3.028 3129.7 3.008 3430.3 2.950 2031.6 2.831 1432.5 2.755 2633.9 2.644 1135.5 2.529 1737.2 2.417 1438.7 2.327 1741.0 2.201 1143.6 2.076 944.5 2.036 949.2 1.852 1449.4 1.845 1149.6 1.838 1153.4 1.716 953.6 1.707 955.8 1.647 11______________________________________
EXAMPLE 36E
(a) TiAPSO-16, as referred to herein in both the as-synthesized and calcined form, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XI-E below:
TABLE XI-E______________________________________2.theta. d,(.ANG.) Relative Intensity______________________________________11.4 7.75 m-vs18.7 4.75 m21.9-22.1 4.05-4.02 m-vs26.4-26.5 3.370-3.363 m29.6-29.8 3.018-3.002 m29.9 2.984 m30.1 2.971 m______________________________________
(b) The TiAPSO-16 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the X-ray powder diffraction pattern of Table XII-E below:
TABLE XII-E______________________________________2.theta. d,(.ANG.) 100 .times. I/Io______________________________________10.5 8.41 511.4 7.75 72-10018.7 4.75 25-5921.1 4.21 321.9-22.1 4.05-4.02 56-10022.8-22.9 3.90-3.89 10-1523.3 3.818 325.0 3.561 625.4-25.5 3.506-3.489 13-1726.4-26.5 3.370-3.363 20-2326.6 3.346 1626.9-27.1 3.314-3.290 4-1528.9-29.1 3.088-3.073 12-1329.6-29.8 3.018-3.002 22-2729.9 2.984 2430.1 2.971 2332.5-32.7 2.755-2.739 3-434.4-34.8 2.607-2.581 3-537.3-37.6 2.411-2.394 4-537.8-37.9 2.380-2.373 8-1438.2-38.4 2.356-2.343 539.5 2.282 3-439.7-39.8 2.270-2.265 3-540.1 2.247 740.5 2.227 444.4 2.040 347.8-47.9 1.904-1.899 548.0-48.1 1.897-1.893 6-848.2-48.3 1.887-1.885 7-848.4-48.5 1.881-1.876 7-848.8 1.865 5.649.0 1.858 549.2 1.853 454.2 1.692 354.3 1.689 3______________________________________
(c) A portion of the as-synthesized TiAPSO-16 of example 4E was subjected to x-ray analysis. The TiAPSO-16 product was characterized by the x-ray powder diffraction pattern of Table XIII-E, below:
TABLE XIII-E______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________11.4 7.75 7218.7 4.74 5922.1 4.02 10022.9 3.89 1125.3 3.521 1526.4 3.376 1326.6 3.346 1626.9 3.314 1529.1 3.073 1329.8 3.002 2229.9 2.984 2430.1 2.971 2334.8 2.581 337.6 2.395 537.9 2.371 1438.4 2.343 539.5 2.282 439.7 2.270 540.1 2.247 740.5 2.227 447.8 1.904 548.1 1.893 848.2 1.887 848.5 1.876 848.8 1.865 649.0 1.858 549.2 1.853 4______________________________________ *peak may contain impurity
(d) The TiAPSO-16 composition of part (c) was calcined at 500.degree. C. in air for 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern shown in Table XIV-E, below:
TABLE XIV-E______________________________________2.theta. d,(.ANG.) 100 .times. I/Io______________________________________10.5 8.41 511.4 7.75 10018.7 4.75 2521.1 4.27 321.9 4.05 5622.8 3.90 1025.0 3.561 6 25.4* 3.506 1425.5 3.489 1326.4 3.370 2028.9 3.088 1229.7 3.007 2734.6 2.594 537.6 2.391 537.9 2.373 938.2 2.356 548.0 1.897 648.3 1.885 7______________________________________ *peak may contain impurity
EXAMPLE 37E
(a) TiAPSO-34, as referred to herein in both the as-synthesized and calcined forms, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XV-E below:
TABLE XV-E______________________________________2.theta. d,(.ANG.) Relative Intensity______________________________________9.4-9.5 9.41-9.31 vs12.9-13.0 6.86-6.81 w-m16.0-16.2 5.54-5.47 w-m20.5-20.8 4.33-4.27 m-vs30.5-30.9 2.931-2.894 m31.5-31.6 2.840-2.831 vw-m______________________________________
(b) The TiAPSO-34 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern of Table XVI-E below:
TABLE XVI-E______________________________________2.theta. d,(.ANG.) 100 .times. I/Io______________________________________9.4-9.5 9.41-9.31 10012.9-13.0 6.86-6.81 16-3114.0-14.1 6.33-6.28 7-1617.8-17.9 4.98-4.96 16-2319.2 4.62 1020.5-20.8 4.33-4.27 38-9722.1-22.2 4.02-4.00 8-923.1-23.3 3.85-3.82 8-1425.0-25.1 3.562-3.548 17-2725.8-26.2 3.453-3.401 19-2127.5-27.9 3.243-3.198 7-1028.2-28.3 3.164-3.153 7-1229.5-29.8 3.028-2.998 8-1230.5-30.9 2.931-2.894 31-3931.1-31.3 2.876-2.858 Sh-2931.5-31.6 2.840-2.831 8-3232.3-32.4 2.772-2.763 6-733.2 2.698 533.8 2.652 534.4-34.9 2.607-2.571 8-935.0 2.564 336.1-36.2 2.488-2.481 6-738.8 2.321 339.6-39.8 2.276-2.265 5-740.2 2.243 543.0 2.103 543.4 2.085 747.5 1.914 548.9-49.2 1.863-1.852 5-849.8 1.831 550.9-51.0 1.794-1.791 7-851.5-51.6 1.774-1.771 3-553.1-53.2 1.725-1.722 7-854.4-54.5 1.687-1.684 5-655.8-55.9 1.647-1.645 6-7______________________________________
(c) A portion of the as-synthesized TiAPSO-34 of example 24E was subjected to x-ray analysis. The TiAPSO-34 product was characterized by the x-ray powder diffraction pattern of Table XVII-E below:
TABLE XVII-E______________________________________2.theta. d,(.ANG.) 100 .times. I/Io______________________________________ 9.4 9.41 10012.9 6.86 1614.0 6.33 1616.0 5.54 5017.9 4.96 2320.5 4.33 9722.1 4.02 823.1 3.85 825.1 3.548 2725.8 3.453 2127.5 3.243 728.3 3.153 729.5 3.028 830.5 2.931 3931.1 2.876 2931.6 2.831 832.4 2.763 733.2 2.698 533.8 2.652 534.4 2.607 835.0 2.564 336.2 2.481 738.8 2.321 339.6 2.276 743.0 2.103 543.4 2.085 747.5 1.914 548.9 1.863 849.8 1.831 550.9 1.794 751.6 1.771 353.1 1.725 754.4 1.687 555.8 1.647 7______________________________________
(d) The TiAPSO-34 compositions of example 24E was calcined at 500.degree. C. in air for 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern shown in Table XVIII-E, below:
TABLE XVIII-E______________________________________2.theta. d,(.ANG.) 100 .times. I/Io______________________________________ 9.5 9.31 10013.0 6.81 3114.1 6.28 716.2 5.47 1917.9 4.96 1619.2 4.62 1020.8 4.27 3822.2 4.00 923.3 3.82 1425.0 3.562 1726.2 3.401 1927.9 3.198 1028.2 3.164 1229.8 2.998 1230.9 2.894 3131.3 2.858 sh32.4 2.763 934.9 2.571 936.2 2.481 739.8 2.265 540.2 2.243 549.2 1.852 551.0 1.791 7______________________________________
EXAMPLE 38E
(a) TiAPSO-35, as referred to herein in both the as-synthesized and calcined forms, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIX-E below:
TABLE XIX-E______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________10.9-11.1 8.12-7.97 m13.3-13.7 6.66-6.46 m17.3-17.4 5.13-5.10 w-m20.8-21.1 4.27-4.21 m21.9-22.2 4.06-4.00 m-vs28.3-28.7 3.153-3.110 m______________________________________
(b) The TiAPSO-35 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern of Table XX-E below:
TABLE XX-E______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________8.6-8.8 10.28-10.05 13-1410.9-11.1 8.12-7.97 36-7413.3-13.7 6.66-6.46 20-3915.9-16.1 5.57-5.51 11-1517.3-17.4 5.13-5.10 17-7517.6-17.7 5.04-5.01 13-1720.8-21.1 4.27-4.21 25-4921.9-22.2 4.06-4.00 65-10023.2-23.7 3.83-3.75 22-3224.9-25.2 3.58-3.534 19-3026.6-26.9 3.363-3.314 19-3528.3-28.7 3.153-3.110 30-4829.1-29.2 3.069-3.058 11-1529.6-29.7 3.018-3.008 6-3931.5-31.7 2.840-2.823 9-1132.1-32.7 2.788-2.739 30-4134.3-34.6 2.614-2.592 11-1735.0-35.1 2.564-2.557 4-535.8-35.9 2.508-2.501 5-637.8-38.0 2.380-2.368 9-1339.5 2.281 4-540.9 2.206 3-441.9 2.156 642.1-42.6 2.146-2.122 5-642.7 2.118 4-648.4-48.5 1.881-1.877 9-1349.0 1.859 5-650.1 1.821 10-1155.0-55.1 1.670-1.667 9-1355.4-55.5 1.658-1.656 9-10______________________________________
(c) A portion of the as-synthesized TiAPSO-35 of example 30E was subjected to x-ray analysis. The TiAPSO-35 product was characterized by the x-ray powder diffraction pattern of Table XXI-E below:
TABLE XXI-E______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________8.6 10.28 1310.9 8.12 3611.4* 7.76 613.3 6.66 2115.9 5.57 1117.3 5.13 7517.7 5.01 1318.6* 4.77 620.8 4.27 4921.9 4.06 10022.6* 3.93 923.2 3.83 3224.9 3.58 1925.2* 3.534 2826.9 3.314 1928.3 3.153 4729.1 3.069 1129.7 3.008 631.5 2.840 932.1 2.788 3834.3 2.614 1135.0 2.564 435.9 2.501 637.8 2.380 939.5 2.281 440.9 2.206 441.9 2.156 642.6 2.122 642.7 2.118 644.7* 2.027 647.6* 1.910 1148.4 1.881 949.0 1.859 649.6* 1.838 750.1 1.821 1154.0* 1.698 655.0 1.670 955.4 1.658 9______________________________________ *peak may contain an impurity
(d) The calcined TiAPSO-35 compositions of example 2E was calcined at 600.degree. C. in air for 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern shown in Table XXII-E, below.
TABLE XXII-E______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________8.8 10.05 1311.1 7.97 7411.5* 7.69 10013.7 6.46 3917.6 5.04 1718.9* 4.70 2621.1 4.21 2622.2 4.00 6523.1* 3.85 2623.7 3.75 2225.2 3.534 3026.6 3.363 3527.4* 3.255 2628.7 3.110 3529.6* 3.018 3929.8* 2.998 4432.7 2.739 3034.6 2.592 1738.0 2.368 1348.5 1.877 1355.1 1.667 13______________________________________ *peak may contain an impurity
EXAMPLE 39E
(a) TiAPSO-44, as referred to herein in both the as-synthesized and calcined forms, have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXIII-E below:
TABLE XIX-E______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________9.5 9.30 s16.1 5.49 m20.8 4.27 vs22.0 4.05 m24.5 3.63 m30.9 2.893 m______________________________________
(b) The TiAPSO-44 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern of Table XXIV-E below:
TABLE XXIV-E______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________9.5 9.30 8311.0 8.06 4513.0 6.79 2413.4 6.62 3013.9 6.40 316.1 5.49 5117.4 5.11 4819.0 4.66 520.8 4.27 10021.1 4.22 3622.0 4.05 7722.7 3.92 723.2 3.83 1924.5 3.63 5226.2 3.400 2027.0 3.307 1127.9 3.195 1028.6 3.123 2829.8 3.000 630.3 2.954 1430.9 2.893 5731.7 2.820 632.2 2.777 3032.6 2.745 533.1 2.708 435.0 2.567 435.7 2.519 1138.7 2.328 342.1 2.145 442.6 2.122 543.7 2.073 447.4 1.920 348.2 1.888 1248.8 1.867 851.5 1.775 654.1 1.696 7______________________________________
(c) A portion of the as-synthesized TiAPSO-44 of Example 11E was subjected to X-ray analysis. The TiAPSO-44 product was characterized by the x-ray powder diffraction pattern of Table XXV-E, below:
TABLE XXV-E______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________8.7* 10.21 149.5 9.30 8311.0 8.06 4511.7* 7.57 313.0 6.79 2413.4 6.62 3013.9 6.40 316.1 5.49 5117.4 5.11 4817.8* 4.98 719.0 4.66 520.8 4.27 10021.1 4.22 3621.5* 4.13 1922.0 4.05 7722.7 3.92 723.2 3.83 1923.6* 3.78 324.5 3.63 5225.1* 3.554 825.4* 3.501 425.6* 3.481 326.2 3.400 2027.0 3.307 1127.9 3.195 1028.6 3.123 2829.2* 3.062 529.8 3.000 630.3 2.954 1430.9 2.893 5731.7 2.820 632.2 2.777 3032.6 2.745 533.1 2.708 434.6* 2.595 735.0 2.567 435.1* 2.559 335.7 2.519 1137.9* 2.372 338.7 2.328 342.1 2.145 442.4* 2.134 542.6 2.122 543.0* 2.103 643.7 2.073 447.4 1.920 348.2 1.888 1248.7* 1.871 848.8 1.867 849.7* 1.836 450.4* 1.809 951.5 1.775 654.1 1.696 7______________________________________ *peak may contain an impurity
EXAMPLE 40E
In order to demonstrate the catalytic activity of the TiAPSO compositions, calcined samples of the TiAPSO products of Examples 6E, 13E, and 24E were tested for catalytic cracking of n-butane.
The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm. I.D. In each test the reactor was loaded with particles of the test TiAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The TiAPSO samples were calcined in air (TiAPSO-5 at 600.degree. C. for 2.5 hours; TiAPSO-11 at 600.degree. C. for 1.5 hours; and TiAPSO-34 at 500.degree. C. for 2 hours) to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500.degree. C. for one hour. The feedstock was a helium-n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromotography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation. The pseudo-first-order rate constant (k.sub.A) was calculated to determine the relative catalytic activity of the TiAPSO compositions. The k.sub.A value (cm.sup.3 /g min) obtained for the TiAPSO compositions are set forth, below, in Table XXVI-E:
TABLE XXVI-E______________________________________ TiAPSO k.sub.A______________________________________ TiAPSO-5 0.6 TiAPSO-11 0.5 TiAPSO-34 1.3______________________________________
ZINC-ALUMINUM-PHOSPHORUS-SILICON-OXIDE SIEVES
Molecular sieves containing zinc, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
PREPARATIVE REAGENTS
In the following examples the ZnAPSO compositions were prepared using numerous reagents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:
(a) Alipro: aluminum isopropoxide;
(b) LUDOX-LS: LUDOX-LS is the trade name of DuPont for an aqueous solution of 30 weight percent SiO.sub.2 and 0.1 weight percent Na.sub.2 O;
(c) CATAPAL: Trademark of Condea Corporation for hydrated pseudoboehmite;
(d) H.sub.3 PO.sub.4 : 85 weight percent aqueous phosphoric acid;
(e) ZnAc: Zinc Acetate, Zn(C.sub.2 H.sub.3 O.sub.2).sub.2 .multidot.4H.sub.2 O;
(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(h) TMAOH: Tetramethylammonium hydroxide pentahydrate, (CH.sub.3).sub.4 NOH.multidot.5H.sub.2 O;
(i) TPAOH: 40 weight percent aqueous solution of tetrapropylammonium hydroxide, (C.sub.3 H.sub.7).sub.4 NOH;
(j) Pr.sub.2 NH: di-n-propylamine, (C.sub.3 H.sub.7).sub.2 NH;
(k) Pr.sub.3 N: Tri-n-propylamine, (C.sub.3 H.sub.7).sub.3 N;
(l) Quin: Quinuclidine, (C.sub.7 H.sub.13 N);
(m) C-hex: cyclohexylamine; and
(n) DEEA: diethylethanolamine, (C.sub.2 H.sub.5).sub.2 NC.sub.2 H.sub.5 OH.
PREPARATIVE PROCEDURE
The ZnAPSO compositions were prepared by preparing reaction mixtures having a molar composition expressed as:
eR:fZnO:gAl.sub.2 O.sub.3 :hP.sub.2 O.sub.5 :iSiO.sub.2 2:jH.sub.2 O
wherein e, f, g, h, i and j represent the moles of template R, zinc (expressed as the oxide), Al.sub.2 O.sub.3, P.sub.2 O.sub.5 (H.sub.3 PO.sub.4 expressed as P.sub.2 O.sub.5), SiO.sub.2 and H.sub.2 O, respectively. The values for e, f, g, h, i and j were as set forth in the hereinafter discussed preparative examples where "j" was 50 in each example, and "e" was 1.0.
The reaction mixtures were prepared by forming a starting reaction mixture comprising the H.sub.3 PO.sub.4 and a portion of the water. This mixture was stirred and the aluminum source added. The resulting mixture was blended until a homogeneous mixture was observed. The LUDOX LS was then added to the resulting mixture and the new mixture blended until a homogeneous mixture was observed. The zinc source (zinc acetate) was dissolved in the remaining water and combined with the first mixture. The combined mixture was blended until a homogenous mixture was observed. The organic templating agent was added to this mixture and blended for about two to four minutes until a homogenous mixture was observed. The resulting mixture (final reaction mixture) was placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at an effective temperature for an effective time. All digestions were carried out at the autogeneous pressure. The products were removed from the reaction vessel cooled and evaluated as set forth hereinafter.
EXAMPLES 1F TO 41F
ZnAPSO molecular sieves were prepared according to the above described procedure and the ZnAPSO products determined by x-ray analysis. The results of preparative examples 1F to 41F are set forth in Tables I-F and II-F. The reactive zinc source was zinc acetate. The reactive aluminum source was Alipro. The reactive phosphorus source was H.sub.3 PO.sub.4. the reactive silicon source was LUDOX-LS. The organic templating agents are set forth in Tables I-F and II-F.
TABLE I-F__________________________________________________________________________Example.sup.2 Template f g h i Temp (.degree.C.) Time (hrs) ZnAPSO Product(s).sup.1__________________________________________________________________________1F Pr.sub.3 N 0.1 1.0 1.0 0.6 150 42 ZnAPSO-36; ZnAPSO-52F Pr.sub.3 N 0.1 1.0 1.0 0.6 150 183 ZnAPSO-36; ZnAPSO-53F Pr.sub.3 N 0.1 1.0 1.0 0.6 200 42 ZnAPSO-5; ZnAPSO-364F Pr.sub.3 N 0.1 1.0 1.0 0.6 200 183 ZnAPSO-5; ZnAPSO-365F Pr.sub.3 N 0.2 0.9 0.9 0.2 150 48 ZnAPSO-5; ZnAPSO-366F TPAOH 0.2 0.9 0.7 0.6 200 165 ZnAPSO-5;7F TPAOH 0.2 0.9 0.7 0.6 200 165 ZnAPSO-58F Pr.sub.2 N 0.1 1.0 1.0 0.6 150 42 ZnAPSO-46; ZnAPSO-39 ZnAPSO-119F Pr.sub.2 NH 0.1 1.0 1.0 0.6 150 183 ZnAPSO-39; ZnAPSO-11 ZnAPSO-4610F Pr.sub.2 NH 0.1 1.0 1.0 0.6 200 42 ZnAPSO-11; ZnAPSO-46 ZnAPSO-3911F Pr.sub.2 NH 0.1 1.0 1.0 0.6 200 183 ZnAPSO-11; ZnAPSO-39 ZnASPO-4612F Pr.sub.2 NH 0.2 0.9 0.7 0.6 150 41 ZnAPSO-46; ZnAPSO-3113F Pr.sub.2 NH 0.2 0.9 0.7 0.6 150 145 ZnAPSO-31; ZnAPSO-4614F Pr.sub.2 NH 0.2 0.9 0.7 0.6 200 41 ZnAPSO-3115F Pr.sub.2 NH 0.2 0.9 0.7 0.6 200 145 ZnAPSO-31__________________________________________________________________________ .sup.1 Major species as identified by xray powder diffraction pattern of product, except that when two or more species were identified the species are listed in the order of their predominance in the product .sup.2 AlPO.sub.4 -31 (as described in U.S. Pat. No. 4,310,440) employed as seed crystals in examples 12F to 15F.
TABLE II-F__________________________________________________________________________Example Template f g h i Temp (.degree.C.) Time (hrs) ZnAPSO Product(s).sup.1__________________________________________________________________________16F TEAOH 0.1 1.0 1.0 0.6 100 134 ZnAPSO-3417F TEAOH 0.1 1.0 1.0 0.6 100 251 ZnAPSO-3418F TEAOH 0.1 1.0 1.0 0.6 150 134 ZnAPSO-5; ZnAPSO-3419F TEAOH 0.1 1.0 1.0 0.6 150 251 ZnAPSO-34; Znapso-520F TEAOH 0.1 1.0 1.0 0.6 200 134 ZnAPSO-5; ZnAPSO-3421F TEAOH 0.1 1.0 1.0 0.6 200 251 ZnAPSO-34; ZnAPSO-522F TEAOH 0.1 0.95 0.7 0.6 100 17 ZnAPSO-3423F TEAOH 0.1 0.95 0.7 0.6 100 66 ZnAPSO-3424F TEAOH 0.1 0.95 0.7 0.6 100 166 ZnAPSO-3425F TEAOH 0.1 0.95 0.7 0.6 100 66 ZnAPSO-3426F TMAOH 0.2 0.9 0.7 0.6 150 46 ZnAPSO-20; ZnAPSO-4327F TMAOH 0.2 0.9 0.7 0.6 150 165 ZnAPSO-20; ZnAPSO-4328F TMAOH 0.2 0.9 0.7 0.6 200 46 ZnAPSO-20; ZnAPSO-4329F TMAOH 0.2 0.9 0.7 0.6 200 165 ZnAPSO-20; ZnAPSO-4330F QUIN 0.2 0.9 0.7 0.6 150 40 ZnAPSO-3531F Quin 0.2 0.9 0.7 0.6 150 158 ZnAPSO-3532F Quin 0.2 0.9 0.7 0.6 200 40 ZnAPSO-3533F Quin 0.2 0.9 0.7 0.6 200 158 ZnAPSO-3534F C-hex 0.2 0.9 0.7 0.6 150 40 ZnAPSO-4435F C-hex 0.2 0.9 0.7 0.6 150 158 ZnAPSO-4436F C-hex 0.2 0.9 0.7 0.6 200 40 ZnAPSO-44; ZnAPSO-537F C-hex 0.2 0.9 0.7 0.6 200 158 ZnAPSO-44; ZnAPSO-538F DEEA 0.2 0.9 0.7 0.6 150 40 ZnAPSO-47; ZnAPSO-539F DEEA 0.2 0.9 0.7 0.6 150 158 ZnAPSO-47; ZnAPSO-540F DEEA 0.2 0.9 0.7 0.6 200 40 ZnAPSO-47; ZnAPSO-541F DEEA 0.2 0.9 0.7 0.6 200 158 ZnAPSO-47__________________________________________________________________________ .sup.1 Major species as identified by xray powder diffraction pattern of product, except that when two or more species were identified the species are listed in the order of their predomenance in the product.
EXAMPLE 42F
Samples of the products of examples 4F, 17F, 24F, 33F, 35F and 39F were subjected to chemical analysis. The chemical analysis for each product is given hereinafter with the example in which the ZnAPSO was prepared being given in parenthesis after the designation of the ZnAPSO species.
(a) The chemical analysis for ZnAPSO-5 (Example 4F) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 31.3P.sub.2 O.sub.5 45.7ZnO 2.8SiO.sub.2 5.7Carbon 5.5LOI* 12.8______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.17R; 0.11 ZnO; 1.0 Al.sub.2 O.sub.3 ; 1.05 P.sub.2 O.sub.5 ; 0.31 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.04R (Zn.sub.0.03 Al.sub.0.44 P.sub.0.47 Si.sub.0.07)O.sub.2
(b) The chemical analysis for ZnAPSO-34 (Example 17F) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 32.3P.sub.2 O.sub.5 35.3ZnO 2.8SiO.sub.2 1.6Carbon 5.0LOI* 26.7______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of: 0.16 R; 0.11 ZnO; 1.0 Al.sub.2 O.sub.3 ; 0.79 P.sub.2 O.sub.5 : 0.08 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.04R (Zn.sub.0.03 Al.sub.0.54 P.sub.0.41 Si.sub.0.02)O.sub.2
(c) The chemical analysis for ZnAPSO-34 (Example 24F) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 36.2P.sub.2 O.sub.5 30.3ZnO 3.8SiO.sub.2 3.7Carbon 5.2LOI* 24.0______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.15R; 0.13 ZnO; 1.0 Al.sub.2 O.sub.3 ; 0.60 P.sub.2 O.sub.5 : 0.07 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.04R (Zn.sub.0.04 Al.sub.0.57 P.sub.0.34 Si.sub.0.05)O.sub.2
(d) The chemical analysis of ZnAPSO-35 (Example 33F) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 30.4P.sub.2 O.sub.5 33.2ZnO 5.6SiO.sub.2 7.6Carbon 10.1LOI* 22.1______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.40R; 0.23 ZnO; 1.0 Al.sub.2 O.sub.3 ; 0.78 P.sub.2 O.sub.5 ; 0.42 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.12R (Zn.sub.0.06 Al.sub.0.47 P.sub.0.37 Si.sub.0.10)O.sub.2
(e) The chemical analysis for ZnAPSO-44 (Example 35F) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 27.5P.sub.2 O.sub.5 31.1ZnO 4.8SiO.sub.2 10.6Carbon 11.7LOI* 25.1______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.60R; 0.22 ZnO; 1.0 Al.sub.2 O.sub.3 ; 0.81 P.sub.2 O.sub.5 ; 0.65 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.13R (Zn.sub.0.05 Al.sub.0.44 P.sub.0.36 Si.sub.0.15)O.sub.2
(f) The chemical analysis of ZnAPSO-47 (Example 39F) was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 30.4P.sub.2 O.sub.5 32.6ZnO 5.3SiO.sub.2 6.5Carbon 7.7LOI* 23.4______________________________________ *LOI = Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios of: 0.35R; 0.22 ZnO; 1.0 Al.sub.2 O.sub.3 ; 0.77 P.sub.2 O.sub.5 ; 0.36 SiO.sub.2 ; and a formula (anhydrous basis) of:
0.09R (Zn.sub.0.05 Al.sub.0.49 P.sub.0.37 Si.sub.0.09)O.sub.2
EXAMPLE 43F
EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope was carried out on clear crystals from the products of examples 4F, 24F, 33F, 35F and 39F. Analysis of crystals having a morphology characteristic of the ZnAPSO products gave the following analysis based on relative peak heights:
(a) ZnAPSO-5 (Example 4F):
______________________________________ Average of Spot Probes______________________________________Zn 1Al 44P 50Si 5______________________________________
(b) ZnAPSO-34 (Example 24F):
______________________________________ Average of Spot Probes______________________________________Zn 3Al 45P 46Si 6______________________________________
(c) ZnAPSO-35 (Example 33F):
______________________________________ Average of Spot Probes______________________________________Zn 5Al 43P 46Si 6______________________________________
(d) ZnAPSO-36 (Example 4F):
______________________________________ Average of Spot Probes______________________________________Zn 4Al 42P 50Si 4______________________________________
(e) ZnAPSO-44 (Example 35F):
______________________________________ Average of Spot Probes______________________________________Zn 2Al 43P 39Si 16______________________________________
(f) ZnAPSO-47 (Example 39F):
______________________________________ Average of Spot Probes______________________________________Zn 5Al 42P 44Si 9______________________________________
EXAMPLE 44F
Samples of the ZnAPSO products of examples 4F, 27F, 33F, 35F and 39F were for adsorption capacities evaluated in the as-synthesized form or were calcined in air or nitrogen, to remove at least part of the organic templating agent, as hereinafter set forth. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum at 350.degree. C. prior to measurement. The McBain-Bakr data for the aforementioned calcined ZnAPSO products were:
(a) ZnAPSO-5 (Example 4F):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 99 -183 11.0O.sub.2 3.46 749 -183 14.9neopentane 6.2 100 23.4 3.5cyclohexane 6.0 57 23.4 7.4H.sub.2 O 2.65 4.6 23.2 13.5H.sub.2 O 2.65 16.8 23.5 17.5______________________________________ *calcined in air at 500.degree. C. for 0.75 hours and at 600.degree. C. for 1.25 hours prior to activation.
The above data demonstrate that the pore size of the calcined product is greater than 6.2 .ANG..
(b) ZnAPSO-34 (Example 27F):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 99 -183 14.5O.sub.2 3.46 725 -183 25.8isobutane 5.0 100 22.8 0.8n-hexane 4.3 98 23.3 13.3H.sub.2 O 2.65 4.6 23.1 19.9H.sub.2 O 2.65 17.8 23.1 30.1______________________________________ *calcined in air at 500.degree. C. for 2 hours prior to activation
The above data demonstrate that the pore size of the calcined product is about 4.3 .ANG..
(c) ZnAPSO-35 (Example 33F):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 99 -183 10.2O.sub.2 3.46 725 -183 19.1n-hexane 4.3 98 23.3 8.6isobutane 5.0 100 22.8 0.8H.sub.2 O 2.65 4.6 23.1 17.2H.sub.2 O 2.65 17.8 23.1 26.3______________________________________ *calcined in air at 500.degree. C. for 1.75 hours prior to activation
The above data demonstrate that the pore size of the calcined product is about 4.3 .ANG..
(d) ZnAPSO-44 (Example 35F):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 99 -183 10.3O.sub.2 3.46 745 -183 19.8n-hexane 4.3 98 23.3 9.7isobutane 5.0 100 22.8 0.8H.sub.2 O 2.65 4.6 23.1 14.0H.sub.2 O 2.65 17.8 23.1 24.0______________________________________ *calcined in air at 500.degree. C. for 67 hours prior to activation
The above data demonstrate that the pore size of the calcined product is about 4.3 .ANG..
(e) ZnAPSO-47 (Example 39F):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________O.sub.2 3.46 99 -183 13.9O.sub.2 3.46 725 -183 23.0isobutane 5.0 100 23.8 0.7n-hexane 4.3 98 23.3 7.8H.sub.2 O 2.65 4.6 23.1 18.8H.sub.2 O 2.65 17.8 23.1 27.0______________________________________ *calcined in air at 500.degree. C. for 1.75 hours prior to activation
The above data demonstrate that the pore size of the calcined product is about 4.3 .ANG..
EXAMPLE 45F
(a) ZnAPSO-5, as prepared in example 4F, was subjected to x-ray analysis. ZnAPSO-5 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 7.4 11.91 100 7.9** 11.17 2912.85 6.88 1013.5* 6.56 114.85 5.96 1915.85** 5.60 316.45** 5.39 819.1** 4.65 919.7 4.51 3820.3** 4.38 420.8** 4.27 1021.05 4.22 3021.5** 4.14 521.65** 4.10 522.4 3.973 7322.95** 3.876 323.85** 3.730 124.75 3.596 225.9 3.442 2527.2** 3.279 427.75** 3.212 128.3** 3.154 229.0 3.078 1529.95 2.981 1530.35** 2.947 232.0** 2.798 333.6 2.666 434.45 2.602 1234.8** 2.577 435.45** 2.532 235.9 2.501 136.95 2.434 337.7 2.386 741.45* 2.177 242.2 2.141 342.8 2.112 143.4 2.085 145.0 2.013 147.6 1.910 451.4 1.778 251.95 1.760 155.6* 1.654 2______________________________________ *peak may contain impurity **impurity peak
(b) A portion of the as-synthesized ZnAPSO-5 of part (a) was calcined in air at 500.degree. C. for about 0.75 hours and then in air at 600.degree. C. for about 1.5 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 7.45 11.91 100 7.85* 11.23 21 8.2* 10.79 712.9 6.87 2013.45* 6.57 314.9 5.95 616.5* 5.37 519.35* 4.58 519.75 4.49 2420.3 4.38 1020.7 4.29 421.1 4.21 2821.4 4.14 1122.4 3.962 6922.75* 3.907 524.85 3.584 226.0 3.430 2427.25* 3.275 427.45* 3.252 227.8* 3.207 228.15* 3.168 328.35* 3.146 229.1 3.068 1630.1 2.970 1433.7 2.658 334.6 2.592 1335.45* 2.532 437.05 2.427 337.85 2.378 642.4 2.132 247.8 1.903 251.5 1.774 355.8 1.647 1______________________________________ *Impurity Peak
(c) The ZnAPSO-5 compositions are generally characterized by the data of Table III-F below.
TABLE III-F______________________________________2.theta. d (.ANG.) Relative Intensity______________________________________7.2-7.4 12.28-11.91 vs19.4-19.8 4.58-4.48 m21.0-21.2 4.23-4.19 m22.3-22.5 3.971-3.952 m-s25.7-26.0 3.466-3.427 w-m______________________________________
(d) The ZnAPSO-5 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table IV-F, below.
TABLE IV-F______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________7.2-7.4 12.28-11.91 10012.6-13.0 7.03-6.81 8-2114.6-14.9 6.07-5.95 9-2019.4-19.8 4.58-4.48 24-3821.0-21.2 4.23-4.19 20-3522.3-22.5 3.971-3.952 47-8224.7-24.9 3.604-3.576 1-225.7-26.0 3.466-3.427 18-2728.9-29.1 3.089-3.069 10-2029.9-30.1 2.988-2.969 12-1733.6-33.8 2.667-2.652 3-434.4-34.6 2.607-2.592 10-1436.9-37.0 2.436-2.430 2-337.6-37.9 2.392-2.374 5-841.45 2.177 0-242.2-42.4 2.141-2.132 2-342.8 2.113 0-143.4 2.090 0-145.0 2.014 0-147.5-47.8 1.914-1.903 2-451.3-51.6 1.781 2-351.95 1.760 0-155.5-55.8 1.656-1.647 0-2______________________________________
EXAMPLE 46F
(a) ZnAPSO-11, as prepared in example 10F was subjected to x-ray analysis. ZnAPSO-11 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 6.6** 13.44 10 7.7** 11.46 97 8.1 10.89 26 8.45** 10.44 6 9.45* 9.35 6013.3* 6.66 2213.8** 6.43 414.9** 5.94 515.3** 5.80 815.7 5.64 2416.2 5.47 316.65** 5.33 718.35** 4.83 1619.0 4.66 419.8** 4.49 420.45* 4.35 2921.1* 4.20 10021.55** 4.123 2422.2* 4.008 3222.75 3.905 8523.2 3.830 4524.2** 3.674 524.45** 3.643 324.8 3.590 526.55 3.355 1426.8* 3.327 1227.8** 3.212 428.7* 3.109 2029.05* 3.075 529.8* 3.000 1130.15* 2.966 1130.75** 2.909 331.1** 2.874 531.6 2.832 632.85* 2.725 1134.3* 2.615 734.5** 2.598 535.9* 2.501 636.55* 2.459 537.85* 2.377 1039.7* 2.270 143.0* 2.103 444.85 2.022 348.85* 1.864 350.8 1.797 154.8 1.675 1______________________________________ *Peak may contain impurity **Impurity Peak
(b) The ZnAPSO-11 compositions are generally characterized by the data of Table V-F below.
TABLE V-F______________________________________2.theta. d (.ANG.) Relative Intensity______________________________________9.35-9.45 9.44-9.35 m13.15-13.35 6.67-6.63 m 21.1-21.25 4.21-4.19 s-vs22.75-22.85 3.911-3.896 s-vs23.15-23.3 3.839-3.819 w-m26.8-26.9 3.327-3.313 w-m______________________________________
(c) The ZnAPSO-11 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table VI-F, below:
TABLE VI-F______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.05-8.1 10.98-10.92 8-269.35-9.45 9.44-9.35 54-7213.15-13.35 6.67-6.63 22-4015.65-15.75 5.66-5.62 10-2716.05-16.2 5.53-5.47 0-319.0 4.66 0-419.85 4.49-4.46 4-1420.4-20.5 4.35-4.33 19-38 21.1-21.25 4.21-4.19 83-100 22.1-22.25 4.018-3.998 12-3222.75-22.85 3.911-3.896 85-10023.15-23.3 3.839-3.819 12-4526.45-26.55 3.369-3.354 8-1426.8-26.9 3.327-3.313 12-4028.7-28.8 3.111-3.100 20-3629.75-29.85 3.005-2.993 11-2331.6-31.8 2.832-2.813 0-10 32.8-32.95 2.731-2.719 7-1534.2-34.3 2.620-2.615 6-935.85-36.0 2.503-2.495 6-1236.45-36.55 2.464-2.459 4-837.65-37.7 2.389-2.387 0-737.85 2.377 0-1039.7 2.271 0-1 43.0-43.05 2.103-2.100 0-444.85-44.9 2.022-2.018 0-348.75-48.85 1.867-1.864 0-350.8-50.9 1.797-1.794 0-354.8 1.675 0-1______________________________________
EXAMPLE 47F
(a) ZnAPSO-20, as prepared in example 29F, was subjected to x-ray analysis. ZnAPSO-20 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________12.35* 7.17 613.9 6.37 4714.35* 6.16 214.5* 6.10 114.65* 6.04 114.85* 5.96 119.75 4.50 4020.8* 4.27 121.05* 4.22 121.7* 4.09 322.1 4.024 224.25 3.672 10024.85* 3.582 127.0* 3.302 528.05 3.181 1228.65* 3.116 131.45 2.845 1232.45* 2.758 134.55 2.596 2037.45 2.402 238.4* 2.248 140.1 2.344 442.65 2.121 445.13* 2.009 147.4 1.917 549.35* 1.846 151.8 1.765 9______________________________________ *Impurity peak
(b) The ZnAPSO-20 compositions are generally characterized by the data of Table VII-F below:
TABLE VII-F______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________13.85-14.0 6.39-6.33 m19.65-19.8 4.52-4.48 m24.15-24.3 3.685-3.663 vs 28.0-28.15 3.187-3.170 w31.35-31.5 2.853-2.840 w 34.5-34.65 2.600-2.589 w-m______________________________________
(c) The ZnAPSO-20 compositions for which x-ray powder diffraction data have been obtained to data have patterns which are characterized by the x-ray powder diffraction pattern shown in Table VIII-F, below:
TABLE VIII-F______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________13.85-14.0 6.39-6.33 45-4719.65-19.8 4.52-4.48 40-41 22.0-22.15 4.040-4.013 2-324.15-24.3 3.685-3.663 100 28.0-28.15 3.187-3.170 12-1331.35-31.5 2.853-2.840 11-12 34.5-34.65 2.600-2.589 16-2037.35-37.5 2.408-2.398 2 40.0-40.2 2.254-2.243 442.55-42.7 2.125-2.118 447.35-47.5 1.920-1.914 551.75-51.9 1.767-1.762 8-9______________________________________
EXAMPLE 48F
(a) ZnAPSO-31, as prepared in example 14F, was subjected to x-ray analysis. ZnAPSO-31 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________ 6.6** 13.40 14 7.7** 11.45 10 8.1** 10.94 11 8.5 10.40 50 9.5* 9.32 8 9.85* 8.96 212.45** 7.12 2513.4 6.60 1017.05 5.21 517.4** 5.10 318.25 4.86 820.3 4.38 5221.3* 4.17 1621.6** 4.11 1022.0 4.036 3022.6 3.394 10023.55* 3.779 224.25** 3.668 325.15* 3.543 427.0** 3.302 327.75* 3.213 1227.95 3.192 1328.2* 3.162 428.7** 3.109 329.75 3.004 1030.3 2.950 431.75 2.810 2032.95 2.718 434.2** 2.623 335.15 2.554 1235.7* 2.515 335.9* 2.500 336.2 2.481 437.25* 2.413 337.65* 2.390 238.25 2.353 339.3 2.291 240.3 2.238 245.0* 2.014 246.6 1.949 447.4** 1.918 248.6 1.873 251.5 1.774 7______________________________________ *peak may contain impurity **impurity peak
(b) The ZnAPSO-31 compositions are generally characterized by the data of Table IX-F below:
TABLE IX-F______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________8.4-8.5 10.53-10.40 m20.2-20.3 4.40-4.37 m21.3 4.171 w22.0 4.036 m22.5-22.6 3.952-3.934 vs 31.6-31.75 2.831-2.820 w-m______________________________________
(c) The ZnAPSO-31 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table X-F, below:
TABLE X-F______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.4-8.5 10.53-10.40 50-539.45-9.5 9.35-9.32 7-813.2-13.4 6.76-6.60 10-11 18.2-18.25 4.87-4.86 5-820.2-20.3 4.39-4.37 49-5221.3 4.171 16-1822.0 4.036 3022.5-22.6 3.952-3.934 10026.9-27.0 3.314-3.302 3-727.95-28.25 3.192-3.529 13-1729.6-29.7 3.018-3.008 8-1030.2-30.3 2.959-2.950 0-4 31.6-31.75 2.831-2.820 18-20 32.95 2.718 4-935.15-35.2 2.554-2.550 1236.1-36.2 2.489-2.481 4-737.25-37.35 2.413-2.409 2-3 38.25 2.353 339.3 2.291 240.3 2.238 2 46.6-46.65 1.949-1.948 4-6 47.4-47.45 1.918-1.916 2-451.5 1.774 7______________________________________
EXAMPLE 49F
(a) ZnAPSO-34, as prepared in example 24F, was subjected to x-ray analysis. ZnAPSO-34 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
TABLE XIII-F______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________9.6 9.19 10012.95 6.84 1614.2 6.25 1416.1 5.50 4218.1 4.90 2220.65 4.30 9122.4 3.978 523.15 3.842 525.3 3.521 2525.9 3.437 1827.7 3.218 528.45 3.135 629.65 3.015 530.6 2.920 3331.3 2.856 2332.5 2.755 234.45 2.602 736.4 2.468 538.8 2.320 439.75 2.267 543.15 2.097 443.55* 2.077 447.65 1.908 549.10 1.856 849.9 1.827 451.0 1.791 453.15 1.723 354.65 1.679 355.9 1.645 3______________________________________ *impurity peak
(b) A portion of the as-synthesized ZnAPSO-34 of part (a) was calcined in air at 500.degree. C. for about 2 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________9.55 9.27 10012.95 6.85 2416.15 5.49 1317.95 4.94 1020.75 4.28 3022.2 4.004 223.25 3.828 525.2 3.533 926.15 3.411 1228.45 3.138 430.9 2.896 1631.35 2.852 9______________________________________
(c) The ZnAPSO-34 compositions are generally characterized by the data of Table XI-F below.
TABLE XI-F______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________9.4-9.8 9.41-9.03 m-vs12.7-13.2 6.97-6.71 w-m15.8-16.2 5.61-5.47 w-m20.5-20.9 4.33-4.25 m-vs25.0-25.3 3.562-3.520 vw-m30.5-30.9 2.931-2.894 w-m______________________________________
(d) The ZnAPSO-34 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XII-F, below:
TABLE XII-F______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________9.4-9.8 9.41-9.03 77-10012.7-13.2 6.97-6.71 16-3114.0-14.3 6.33-6.19 0-2215.8-16.2 5.61-5.47 16-4717.8-18.2 4.98-4.87 13-2920.5-20.9 4.33-4.25 36-10022.2-22.5 4.004-3.952 5.823.0-23.3 3.867-3.818 5-625.0-25.3 3.562-3.520 9-32 25.7-26.25 3.466-3.395 12-2027.45-27.7 3.249-3.220 5-8 28.1-28.45 3.175-3.137 4-829.4-29.8 3.038-2.998 0-530.5-30.9 2.931-2.894 16-35 31.0-31.65 2.885-2.827 9-2532.2-32.5 2.780-2.755 0-234.3-34.8 2.614-2.578 5-836.1-36.4 2.488-2.468 0-538.65-38.8 2.330-2.321 0-439.5-39.8 2.281-2.265 4-743.0-43.4 2.103-2.085 447.5-48.0 1.914-1.895 3-648.8-49.1 1.866-1.855 8-1049.9 1.859 0-450.8-51.0 1.797-1.791 0-4 53.1-53.15 1.725-1.723 0-354.5-54.8 1.684-1.675 0-355.8-55.9 1.647-1.645 0-4______________________________________
EXAMPLE 50F
(a) ZnAPSO-35, as prepared in example 33F, was subjected to x-ray analysis. ZnAPSO-35 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.6 10.27 2010.5* 8.44 sh10.95 8.08 4711.35 7.80 413.30 6.66 3915.9 5.57 1017.3 5.13 7217.8 4.98 sh21.15 4.20 4821.9 4.06 10023.15 3.841 1923.65 3.762 325.05 3.552 426.8 3.325 2228.7 3.107 3029.1 3.069 sh32.1 2.788 4334.75 2.582 935.5 2.530 335.8 2.507 537.75 2.382 539.35 2.889 442.35 2.134 643.15 2.096 448.6 1.873 1149.4 1.845 851.55 1.773 655.3 1.661 6______________________________________ *impurity peak
(b) A portion of the as-synthesized ZnAPSO-35 of part (a) was calcined in air at 500.degree. C. for about 1.75 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________7.45* 11.85 108.7 10.15 2211.0 8.04 9113.5 6.55 10017.45 5.08 3521.0 4.23 2122.15 4.011 6023.5 3.782 1925.15 3.542 1327.2 3.278 2028.6 3.122 2829.35 3.041 1432.45 2.759 28______________________________________ *impurity peak
(c) The ZnAPSO-35 compositions obtained to date have patterns which are generally characterized by the data of Table XIII-F below.
TABLE XIII-F______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________10.8-11.0 8.19-8.04 m-vs13.30-13.5 6.66-6.56 m-vs 17.2-17.45 5.16-5.08 m20.95-21.2 4.24-4.19 m 21.9-22.15 4.06-4.01 m-vs32.0-32.5 2.797-2.755 m______________________________________
(d) The ZnAPSO-35 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XIV-F below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________8.6-8.7 10.27-10.16 18-2210.8-11.0 8.19-8.04 43-9111.35 7.80 0-413.30-13.5 6.66-6.56 39-10015.8-15.9 5.61-5.57 0-10 17.2-17.45 5.16-5.08 35-7517.8-17.9 4.98-4.96 0-sh20.95-21.2 4.24-4.19 21-49 21.9-22.15 4.06-4.01 60-10023.0-23.5 3.867-3.786 0-1923.65 3.762 0-324.85-25.15 3.583-3.541 4-1326.6-27.2 3.351-3.278 20-2228.5-28.8 3.132-3.100 26-30 29.1-29.35 3.069-3.043 sh-1432.0-32.5 2.797-2.755 28-4334.55-34.9 2.596-2.571 0-935.7-35.8 2.515-2.507 0-537.75 2.382 0-539.35 2.889 0-4 42.1-42.35 2.146-2.134 0-643.0-43.2 2.103-2.094 0-448.5-48.7 1.877-1.870 0-1149.35-49.4 1.847-1.845 0-851.4-51.6 1.778-1.771 0-755.3-55.4 1.661-1.658 0-6______________________________________
EXAMPLE 51F
(a) ZnAPSO-36, as prepared in example 1F, was subjected to x-ray analysis. ZnAPSO-36 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________7.45** 11.85 767.95 11.13 1008.2 10.76 sh12.9** 6.87 313.6 6.52 414.9** 5.95 1015.9 5.58 1016.45 5.38 2519.1 4.64 1619.75** 4.50 1520.8* 4.27 3221.05** 4.22 sh21.75 4.09 1422.1 4.025 1422.4* 3.966 2423.0 3.863 323.95 3.716 525.9** 3.440 927.3 3.269 1128.35 3.147 729.05* 3.074 930.0** 2.978 830.35 2.944 432.0 2.796 833.2 2.698 133.65** 2.663 134.5** 2.599 634.8 2.575 735.9 2.500 237.75 2.383 240.3 2.237 241.45 2.178 242.2 2.142 147.6* 1.910 251.35 1.779 254.0 1.697 155.65 1.652 2______________________________________ *peak may contain impurity **impurity peak
(b) The ZnAPSO-36 compositions obtained to date have patterns which are generally characterized by the data of Table XV-F below.
TABLE XV-F______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________7.45-8.0 11.14-11.04 vs16.45-16.5 5.38-5.36 w-m19.1-19.2 4.65-4.62 w-m20.8-20.9 4.28-4.25 w-m21.75-21.8 4.09-4.08 w22.05-22.15 4.027-4.017 w______________________________________
(c) The ZnAPSO-36 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XVI-F below:
TABLE XVI-F______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________7.45-8.0 11.14-11.04 1008.2-8.3 10.76-10.68 0-sh13.55-13.6 6.53-6.50 3-415.85-15.95 5.60-5.56 10-1216.45-16.5 5.38-5.36 18-3119.1-19.2 4.65-4.62 19-2220.8-20.9 4.28-4.25 17-3921.75-21.8 4.09-4.08 10-1722.05-22.15 4.027-4.017 14-17 23.0-23.05 3.865-3.859 3-423.85-24.0 3.728-3.707 3-627.25-27.35 3.273-3.260 9-1528.3-28.4 3.152-3.142 6-930.1-30.4 2.970-2.940 4-631.95-32.1 2.803-2.788 6-1133.2-33.6 2.698-2.665 1-234.75-34.9 2.580-2.572 7-1035.85-35.95 2.504-2.497 2-637.75-37.8 2.384-2.380 240.15-40.4 2.246-2.232 1-341.45-41.5 2.180-2.176 1-242.2-42.3 2.142-2.137 0-2 51.4-51.45 1.779-1.776 254.0 1.697 0-155.4-55.8 1.658-1.648 1-2______________________________________
EXAMPLE 52F
(a) ZnAPSO-39, as referred to in example 9F, was subjected to x-ray analysis. ZnAPSO-39 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________6.5** 13.59 177.65** 11.56 1738.05** 10.99 128.35** 10.58 49.35* 9.44 7213.25* 6.67 3513.7** 6.46 814.9** 5.95 815.2** 5.82 1215.65** 5.66 1216.6** 5.34 1318.3 4.85 3619.8** 4.48 420.4** 4.35 1921.1* 4.21 8321.5** 4.13 3622.1** 4.018 1222.75* 3.911 10023.15** 3.839 1923.95** 3.716 424.2** 3.681 924.8** 3.593 326.45** 3.369 826.8* 3.324 2127.75** 3.215 628.2** 3.162 528.7* 3.111 1929.7* 3.005 1530.1* 2.970 2230.6** 2.922 431.05** 2.881 732.8* 2.731 834.3* 2.615 634.55** 2.597 1035.9** 2.502 836.45* 2.464 438.05* 2.365 540.7* 2.217 4______________________________________ *peak may contain impurity **impurity peak
(b) The ZnAPSO-39 compositions are generally characterized by the data of Table XVII-F below.
TABLE XVII-F______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________9.35-9.45 9.46-9.36 m13.15-13.35 6.73-6.63 m18.3-18.4 4.85-4.82 w-m21.1-21.2 4.21-4.19 s-vs22.75-22.85 3.909-3.892 s-vs26.8-26.9 3.389-3.314 w-m______________________________________
(c) The ZnAPSO-39 compositions for which x-ray powder diffraction data have been obtained to data have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XVIII-F below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________9.35-9.45 9.46-9.36 60-7213.15-13.35 6.73-6.63 22-4018.3-18.4 4.85-4.82 16-4021.1-21.2 4.21-4.19 83-10022.75-22.85 3.909-3.892 85-10026.8-26.9 3.389-3.314 12-4028.2-28.3 3.164-3.153 5-828.7-28.8 3.110-3.100 19-2029.7-29.8 3.008-2.998 11-3230.1-30.2 2.979-2.959 11-25 32.8-32.95 2.730-2.718 8-12 34.5-34.65 2.600-2.589 5-636.45-36.5 2.465-2.462 4-1237.85-38.1 2.377-2.362 3-10 40.6-40.95 2.222-2.204 0-4______________________________________
EXAMPLE 53F
(a) ZnAPSO-43, as referred to in example 28F, was subjected to x-ray analysis. ZnAPSO-43 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________12.45 7.11 7614.0* 6.32 19416.95 5.24 819.8* 4.48 16020.95 4.24 1321.15* 4.20 1321.85 4.07 4822.15* 4.010 824.3* 3.659 40027.1 3.291 10028.15* 3.171 5228.75 3.104 431.55* 2.837 4932.55 2.751 2032.75* 2.733 934.25* 2.620 834.65* 2.590 6837.5* 2.399 838.5* 2.340 640.2* 2.244 1641.2 2.190 442.7* 2.117 1645.1 2.010 847.5* 1.914 1849.45* 1.843 751.15 1.787 751.9* 1.761 3653.8 1.704 7______________________________________ *Impurity peak
(b) ZnAPSO-43 compositions are generally characterized by the data of Table XIX-F below:
TABLE XIX-F______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________12.3-12.45 7.20-7.11 m-vs16.8-16.95 5.28-5.23 vw-w21.7-21.85 4.095-4.068 vw-m26.95-27.1 3.308-3.291 s-vs32.4-33.55 2.763-2.751 w-m______________________________________
(c) The ZnAPSO-43 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XX-F below:
TABLE XX-F______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________12.3-12.45 7.20-7.11 66-10016.8-16.95 5.28-5.23 0-1020.8-20.95 4.27-4.24 10-1321.7-21.85 4.095-4.068 0-4826.95-27.1 3.308-3.290 82-10028.65-28.75 3.116-3.105 11-2332.4-32.55 2.763-2.751 18-2041.2 2.191 0-444.95-45.1 2.017-2.010 8-1550.95-51.15 1.792-1.786 0-753.7-53.8 1.710-1.707 0-8______________________________________
EXAMPLE 54F
(a) ZnAPSO-44 as prepared in example 34F, was subjected to x-ray analysis. ZnAPSO-44 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________4.95* 17.93 118.75* 10.09 sh9.25* 9.56 sh9.55 9.25 10013.05 6.77 1313.8 6.41 316.15 5.49 2117.4 5.10 319.05 4.65 719.6* 4.53 220.8 4.27 4621.8 4.08 1822.65 3.923 423.15 3.845 524.45 3.638 4726.25 3.395 1427.3* 3.266 127.9 3.197 729.8 2.999 330.15 2.962 1330.9 2.895 3132.65 2.745 233.0 2.716 634.9 2.571 235.15 2.553 235.6 2.523 938.7 2.329 239.25 2.295 240.1 2.247 142.25 2.139 342.55 2.124 243.7 2.072 148.2 1.887 348.8 1.866 450.4 1.811 552.0 1.759 154.0 1.698 7______________________________________ *Impurity peak
(b) A portion of the as-synthesized ZnAPSO-44 of part (a) was calcined in air at 500.degree. C. for about 67 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________9.6 9.23 10013.0 6.81 3414.05 6.29 516.2 5.48 1617.95 4.95 3020.3** 4.37 2220.8 4.27 5221.4 4.15 3222.3 3.987 722.75* 3.906 723.25 3.826 1024.75** 3.599 525.15 3.538 2226.15 3.406 1128.4 3.142 928.75** 3.107 730.95 2.888 2331.35* 2.852 1535.3* 2.542 9______________________________________ *Peak may contain impurity **Impurity peak
(c) The ZnAPSO-44 compositions are generally characterized by the data of Table XXI-F below:
TABLE XXI-F______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________ 9.4-9.55 9.41-9.26 vs 12.9-13.05 6.86-6.78 vw-m20.65-20.8 4.30-4.27 m21.4-21.8 4.15-4.08 w-m 24.3-25.15 3.663-3.541 m30.75-30.95 2.908-2.889 m______________________________________
(d) The ZnAPSO-44 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXII-F below:
TABLE XXII-F______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________ 9.4-9.55 9.41-9.25 100 12.9-13.05 6.86-6.78 8-34 13.6-14.05 6.51-6.30 3-516.0-16.2 5.54-5.47 14-2117.25-17.95 5.14-4.94 0-618.95-19.05 4.68-4.66 0-520.65-20.8 4.30-4.27 35-5221.4-21.8 4.15-4.08 18-3222.55-22.65 3.943-3.926 423.15-23.25 3.842-3.826 5-10 24.3-25.15 3.663-3.541 22-47 26.2-26.25 3.414-3.395 8-1427.7-28.4 3.220-3.143 7-929.8 2.998- 0-330.05-30.15 2.974 0-1330.75-30.95 2.908-2.889 23-3132.65-32.8 2.743-2.730 0-333.0 2.714 0-634.9 2.571 0-235.15 2.553 0-235.3-35.6 2.543-2.522 9-1038.7 2.327-2.327 0-239.3-40.2 2.292-2.243 0-240.1 2.249 0-142.1-42.3 2.146-2.137 0-342.55 2.127 0-243.7 2.071 0-148.2 1.888 0-348.65-48.8 1.872-1.866 0-550.2-50.4 1.817-1.811 0-552.0 1.759 0-153.8- 54.0 1.704-1.698 0-7______________________________________
EXAMPLE 55F
(a) ZnAPSO-46, as referred to in example 8F was subjected to x-ray analysis. ZnAPSO-46 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________6.6 13.39 87.75 11.42 1008.1** 10.90 39.45** 9.34 1810.2 8.67 113.35* 6.63 1013.8 6.41 414.95 5.92 415.75** 5.62 316.7 5.31 717.5 5.07 118.4** 4.83 1019.85 4.47 320.5* 4.33 621.25** 4.19 2521.6 4.12 1822.25** 3.998 322.8 3.896 3223.3** 3.818 424.05 3.700 324.25* 3.669 525.3* 3.523 126.55** 3.354 326.9 3.313 1027.8 3.207 328.3 3.152 228.8* 3.100 829.85* 2.993 630.2** 2.961 731.15 2.870 331.8* 2.813 132.95* 2.719 334.3* 2.612 234.65** 2.590 336.0* 2.495 336.55 2.459 236.8* 2.442 137.3 2.410 138.1** 2.361 139.7* 2.271 140.95* 2.204 143.2** 2.093 144.1* 2.054 146.1* 1.969 147.65* 1.908 149.45** 1.844 149.65* 1.836 151.55* 1.772 152.45* 1.745 1______________________________________ *Peak may contain impurity **Impurity peak
(b) The ZnAPSO-46 compositions are characterized by the data of Table XXIII-F below:
TABLE XXIII-F______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________ 7.6-7.75 11.63-11.42 vs 13.1-13.35 6.76-6.63 w-m21.5-21.6 4.13-4.12 w-m 22.6-22.85 3.934-3.896 m26.75-27.0 3.333-3.302 w______________________________________
(c) The ZnAPSO-46 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXIV-F below:
TABLE XXIV-F______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________6.5-6.7 13.60-13.19 7-10 7.6-7.75 11.63-11.42 10010.2 8.67 0-1 13.1-13.35 6.76-6.63 10-2013.7-13.8 6.46-6.41 4-514.9-15.0 5.95-5.91 4-5 15.2-15.35 5.83-5.77 5-716.6-16.8 5.34-5.28 717.35-17.5 5.11-5.07 0-119.7-20.0 4.51-4.44 2-320.3-20.5 4.37-4.33 6-1121.5-21.6 4.13-4.12 18-21 22.6-22.85 3.934-3.896 32-58 23.9-24.05 3.723-3.700 2-325.1-25.3 3.548-3.520 0-126.75-27.0 3.333-3.302 10-1227.7-28.0 3.220-3.187 3-428.2-28.3 3.175-3.152 2-328.6-28.9 3.121-3.089 8-1129.7-29.9 3.008-2.988 6-9 31.0-31.15 2.885-2.870 3-431.6-31.8 2.831-2.813 0-132.8-33.2 2.730-2.706 3-434.15-34.4 2.626-2.607 2-435.8-36.0 2.508-2.495 3-436.45-36.55 2.464-2.459 2-337.3-37.7 2.410-2.386 0-239.7 2.271 0-140.9-41.1 2.206-2.196 0-143.85-44.1 2.065-2.054 0-146.1 1.969 0-147.4-47.7 1.918-1.908 0-149.7-49.8 1.834-1.831 0-151.4-51.7 1.778-1.768 0-1 52.2-52.45 1.752-1.745 0-1______________________________________
EXAMPLE 56F
(a) ZnAPSO-47, as referred to in example 38F, was subjected to x-ray analysis. ZnAPSO-47 was determined to have a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth below:
______________________________________2.THETA. d,(.ANG.) 100 .times. I/Io______________________________________7.45* 11.88 29.45 9.35 9312.9 6.87 1713.9 6.38 716.0 5.54 4217.65 5.03 1119.0* 4.67 320.6 4.31 10021.85 4.07 722.4* 3.97 623.0 3.867 1124.75 3.600 2125.9 3.439 2327.65 3.228 1028.0 3.188 329.5 3.029 530.6 2.922 4930.9 2.894 sh31.5 2.839 332.3 2.772 233.3 2.689 334.5 2.600 1034.9 2.573 235.7 2.516 438.4 2.344 339.65 2.273 442.5 2.126 343.3 2.089 244.9 2.019 247.6 1.909 448.6 1.873 550.5 1.807 553.25 1.721 554.5 1.684 256.0 1.642 5______________________________________ *Impurity peak
(b) A portion of the as-synthesized ZnAPSO-47 of part (a) was calcined in air at 500.degree. C. for about 1.75 hours. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________7.5* 11.78 119.65 9.17 10013.05 6.78 2514.15 6.26 316.2 5.46 1018.0 4.93 819.25 4.61 319.8* 4.49 220.85 4.26 2721.25* 4.18 sh22.5* 3.950 823.3 3.816 425.2 3.533 826.2 3.399 1028.0 3.187 228.55 3.126 329.8 2.998 231.0 2.885 1831.4 2.849 sh34.9 2.571 2______________________________________ *Impurity peak
(c) The ZnAPSO-47 compositions are characterized by the date in Table XXV-F below:
TABLE XXV-F______________________________________2.THETA. d, (.ANG.) Relative Intensity______________________________________9.45-9.65 9.35-9.17 vs12.85-13.05 6.89-6.78 w-m15.95-16.2 5.55-5.46 w-m20.55-20.85 4.31-4.26 m-vs25.9-26.2 3.439-3.399 w-m30.55-31.0 2.925-2.885 w-m______________________________________
(d) The ZnAPSO-47 compositions for which x-ray powder diffracton data have been obtained to date have patterns which are characterized by the x-ray powder diffraction pattern shown in Table XXVI-F below:
TABLE XXVI-F______________________________________2.THETA. d, (.ANG.) 100 .times. I/Io______________________________________9.45-9.65 9.35-9.17 93-10012.85-13.05 6.89-6.78 17-2513.85-14.15 6.39-6.26 3-715.95-16.2 5.55-5.46 10-4217.45-18.0 5.09-4.93 2-1120.55-20.85 4.31-4.26 27-100 21.85 4.07 0-722.95-23.3 3.867-3.816 4-1124.75-25.2 3.600-3.533 8-2125.9-26.2 3.439-3.399 16-29 27.6-28.55 3.231-3.126 3-1027.9-28.0 3.196-3.188 0-329.45-29.8 3.031-2.998 2-530.55-31.0 2.925-2.885 18-4930.9-31.4 2.894-2.849 sh31.5 2.839 0-332.3 2.772 0-233.3 2.689 0-334.45-34.9 2.603-2.600 2-1934.9 2.573 0-235.7-35.9 2.516-2.503 0-5 38.4-38.55 2.344-2.336 0-3 39.6-39.65 2.273 0-442.25-42.5 2.139-2.126 0-343.3 2.089 0-244.9 2.019 0-247.6 1.909 0-648.6-48.7 1.873-1.870 0-550.45-50.5 1.807 0-5 53.2-53.25 1.722-1.721 0- 554.5 1.684 0-256.0 1.642 0-5______________________________________
EXAMPLE 57F
In order to demonstrate the catalytic activity of calcined ZnAPSO compositions were tested for catalytic cracking of n-butane using a bench-scale apparatus.
The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm. I.D. In each test the reactor was loaded with particles of the test ZnAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The ZnAPSO samples had been previously calcined in air to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500.degree. C. for one hour. The feedstock was a helium n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.
The pseudo-first-order rate constant (k.sub.A) was calculated to determine the relative catalytic activity of the ZnAPSO compositions. The k.sub.A value (cm.sup.3 /g min) obtained for the ZnAPSO compositions are set forth, below, in Table XXVII-F:
TABLE XXVII-F______________________________________ Prepared inZnAPSO Example No. Rate Constant (k.sub.A)*______________________________________ZnAPSO-5 4F 1.5ZnAPSO-34 24F 12.7ZnAPSO-35 33F 1.0ZnAPSO-44 35F 5.0ZnAPSO-47 39F 5.6______________________________________ *ZnAPSO-5 were calcined prior to in situ activation as follows: (a) ZnAPSO5: in air at 500.degree. C. for 0.75 and at 600.degree. C. for 1.25 hours; (b) ZnAPSO34: in air at 500.degree. C. for 2 hours; (c) ZnAPSO35: in air at 500.degree. C. for 1.75 hours; (d) ZnAPSO44: in air at 500.degree. C. for 67 hours; and (e) ZnAPSO47: in air at 500.degree. C. for 1.75 hours.
COBALT-MANGANESE-ALUMINUM-PHOSPHORUS-SILICON-OXIDE SIEVES
Preparative Reagents
In the following examples the CoMnAPSO compositions were prepared using numerous regents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:
(a) Aiipro: aluminum isopropoxide;
(b) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO.sub.2 and 0.1 weight percent Na.sub.2 O;
(c) H.sub.3 PO.sub.4 : 85 weight percent phosphoric acid;
(d) MnAc: Manganese acetate, Mn(C.sub.2 H.sub.3 O.sub.2).sub.2. 4H.sub.2 O;
(e) CoAc: Cobalt Acetate, Co(C.sub.2 H.sub.3 O.sub.2).sub.2.4H.sub.2 O;
(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide; and
(g) Pr.sub.2 NH: di-n-propylamine, (C.sub.3 H.sub.7).sub.2 NH.
Preparative Procedures
The following preparative examples were carried out by forming a starting reaction mixture by adding the H.sub.3 PO.sub.4 and one half of the quantity of water. To this mixture the aluminum isopropoxide was added. This mixture was then blended until a homogeneous mixture was observed. To this mixture the LUDOX-LS was added and the resulting mixture blended (about 2 minutes) until a homogeneous mixture was observed. A second mixture was prepared using manganese acetate and one half of the remaining water. A third mixture was prepared using cobalt acetate and one half of the remaining water. The three mixtures were admixed and the resulting mixture blended until a homogeneous mixture was observed. The organic templating agent was then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture was observed, i.e. about 2 to 4 minutes. The pH of the mixture was measured and adjusted for temperature. The mixture was then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature All digestions were carried out at the autogeneous pressure.
EXAMPLES 1G to 4G
CoMnAPSO molecular sieves were prepared according to the above identified procedure and the CoMnAPSO products determined by X-ray analysis. The results of examples 1G to 4G are set forth in Table I-G. Examples AG to FG in Table I-G represent reaction mixtures that did not show CoMnAPSO products when determined by X-ray analysis.
TABLE I-G__________________________________________________________________________Example.sup.1 Template Temp (.degree.C.) Time (days) CoMnMgAPSO Product(s).sup.2__________________________________________________________________________1G TEAOH 150 2 CoMnAPSO-34; CoMnAPSO-52G TEAOH 150 7 CoMnAPSO-34; CoMnAPSO-53G Pr.sub.2 NH 200 2 CoMnAPSO-5; CoMnAPSO-114G Pr.sub.2 NH 200 7 CoMnAPSO-5; CoMnAPSO-11AG TEAOH 100 3 --BG TEAOH 100 7 --CG Pr.sub.2 NH 150 2 --.sup. DG.sup.3 Pr.sub.2 NH 150 10 --.sup. EG.sup.3 Pr.sub.2 NH 150 6 --.sup. FG.sup.3 Pr.sub.2 NH 150 15 --__________________________________________________________________________ .sup.1 The reaction mixture comprised: 1.0 R: 0.2 MnO: 0.2 CoO: 0.8 Al.sub.2 O.sub.3 : 0.8 P.sub.2 O.sub.5 : 0.4 SiO.sub.2 : 50 H.sub.2 O where "R" is the template. .sup.2 Major species as identified by xray powder diffraction pattern of product, except that when two species are identified the first species listed is present in an amount equal to or greater than the second specie listed. A "--" indicates that crystalline products were not identified by Xray analysis. .sup.3 X-ray analysis indicated that crystalline product was beginning to form.
EXAMPLE 5G
(a) Samples of the above prepared CoMnAPSO products, as identified in parenthesis, were calcined in air to remove at least part of the organic templating agent of the CoMnAPSO product. The adsorption capacities of each calcined sample were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The samples were activated in a vacuum (less than 0.04 torr) at 350.degree. C. prior to measurement. The McBain-Bakr data were as follows:
(b) CoMnAPSO-34 and CoMnAPSO-5 (Example 2G):
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________Oxygen 3.46 105 -183 13.8Oxygen 3.46 733 -183 18.5Neopentane 6.2 742 23.8 2.6Cyclohexane 6.0 65 23.7 4.6n-hexane 4.3 93 23.4 5.0H.sub.2 O 2.65 4.6 23.4 15.8H.sub.2 O 2.65 19 23.7 23.6______________________________________ *calcined in air at 600.degree. C. for one hour prior to activation
(c) CoMnAPSO-5 and CoMnAPSO-11
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed*______________________________________Oxygen 3.46 105 -183 5.5Oxygen 3.46 733 -183 9.3Neopentane 6.2 742 23.8 2.4Cyclohexane 6.0 65 23.7 5.9H.sub.2 O 2.65 4.6 23.4 7.4H.sub.2 O 2.65 19 23.7 16.2______________________________________ *calcined in air at 600.degree. C. for one hour prior to activation
EXAMPLE 6G
Samples of the as-synthesized products of examples 2G and 4G were subjected to chemical analysis. The chemical analysis for these CoMnAPSOs was:
(a) The chemical analysis for the product of example 2G was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 27.5P.sub.2 O.sub.5 37.7SiO.sub.2 4.98CoO 4.3MnO 5.2Carbon 5.3LOI* 20.5______________________________________ *Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of:
0.057CoO:0.073MnO:0.270Al.sub.2 O.sub.3 :0.266P.sub.2 O.sub.5 :0.083SiO.sub.2
and a formula (anhydrous basis) of:
0.055R(Al.sub.0.420 P.sub.0.414 Si.sub.0.065 Co.sub.0.044 Mn.sub.0.057)O.sub.2.
(b) The chemical analysis for the product of example 4G was:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 26.6P.sub.2 O.sub.5 37.6SiO.sub.2 7.1CoO 5.1MnO 6.0Carbon 1.91LOI* 17.9______________________________________ *Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of:
0.068CoO:0.085MnO:0.261Al.sub.2 O.sub.3 :0.265P.sub.2 O.sub.5 :0.118SiO.sub.2
and a formula (anhydrous basis) of:
0.027R(Al.sub.0.40 P.sub.0.40 Si.sub.0.089 Co.sub.0.051 Mn.sub.0.064)O.sub.2.
EXAMPLE 7G
EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on the products of examples 2G and 4G. Analysis of crystals having a morphology characteristic of each CoMnAPSO product gave the following analysis based on relative peak heights:
(a) Example 2G (CoMnAPSO-5):
______________________________________ Average of Spot Probes______________________________________Al 0.81P 0.98Si 0.18Co 0.10Mn 0.17______________________________________
(b) Example 2G (CoMnAPSO-34):
______________________________________ Average of Spot Probes______________________________________Al 0.82P 0.93Si 0.17Co 0.03Mn 0.03______________________________________
(c) Example 4G (CoMnAPSO-5):
______________________________________ Average of Spot Probes______________________________________Al 0.93P 0.71Si 0.15Co 0.05Mn 0.07______________________________________
(d) Example 4G (CoMnAPSO-11):
______________________________________ Average of Spot Probes______________________________________Al 0.81P 0.95Si 0.15Co 0.03Mn 0.05______________________________________
EXAMPLE 8G
(a) CoMnAPSO-5, as prepared in example 1G, was subjected to x-ray analysis. The CoMnAPSO-5 was determined to have an x-ray powder diffraction pattern characterized by the following data:
______________________________________2.theta. d(.ANG.) (I/Io) .times. 100______________________________________7.5 11.84 679.5* 9.29 10012.9** 6.89 1114.1* 6.29 714.9 5.93 1416.0* 5.54 2218.0* 4.93 1019.8 4.49 1920.6* 4.32 5121.1** 4.22 4022.4 3.96 2825.2* 3.530 1229.1 3.071 629.5* 3.024 330.1 2.968 1030.5* 2.928 1631.3* 2.862 1133.7* 2.659 334.5 2.601 434.6* 2.591 537.8 2.383 647.7** 1.905 348.9* 1.863 249.9* 1.828 250.9* 1.794 255.8 1.647 2______________________________________ *peak may be an impurity **impurity peak and CoMnMgAPSO5
(b) A portion of the as-synthesized CoMnAPSO-5 of example 2G was calcined in air at 600.degree. C. for one (1) hour. The calcined product was characterized by the following x-ray powder diffraction pattern:
______________________________________2.theta. d(.ANG.) (I/Io) .times. 100______________________________________7.5 11.84 329.6* 9.20 10013.0** 6.81 2014.9 5.93 416.2* 5.48 818.0* 4.93 619.3* 4.60 319.8 4.49 820.9** 4.26 2221.2** 4.20 2621.5* 4.13 322.5 3.95 3223.4* 3.81 325.3* 3.520 726.1 3.420 1126.2* 3.396 728.5* 3.129 329.2 3.063 630.2 2.965 631.0* 2.881 1131.5* 2.840 734.7 2.584 434.9 2.568 338.0* 2.368 2______________________________________ *peak may be an impurity **impurity peak and CoMnAPSO5
(c) The species CoMnAPSO-5 is a molecular sieve having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table II-G as follows:
TABLE II-G______________________________________2.theta. d(.ANG.) Relative Intensity______________________________________7.4-7.5 11.95-11.84 m12.9-13.1 6.89-6.76 w-m14.9 5.93 vw-w19.7-19.8 4.51-4.49 vw-w20.9-21.3 4.26-4.17 m22.4-22.5 3.97-3.95 m______________________________________
(d) All of the CoMnAPSO-5 compositions, both as-synthesized and calcined, for which x-ray powder diffraction data have been obtained have patterns which are within the generalized pattern of Table III-G, below:
TABLE III-G______________________________________2.theta. d(.ANG.) (I/Io) .times. 100______________________________________7.4-7.5 11.95-11.84 32-6712.9-13.1 6.89-6.81 11-2014.9 5.93 4-1419.7-19.8 4.51-4.49 8-1920.9-21.3 4.26-4.17 22-4022.4-22.5 3.96-3.95 28-3224.7-24.8 3.60-3.59 625.9-26.1 3.440-3.420 10-1129.0-29.2 3.079-3.063 629.9-30.2 2.988-2.965 6-1034.4-34.7 2.607-2.584 434.9 2.568 337.8 2.383 647.7 1.905 355.8 1.647 2______________________________________
EXAMPLE 9G
(a) The CoMnAPSO-11, prepared in example 3G, was subjected to X-ray analysis. The CoMnAPSO-11 was impure but the CoMnAPSO-11 was determined to have an X-ray powder diffraction pattern characterized by the following data:
______________________________________2.theta. d(.ANG.) (I/Io) .times. 100______________________________________7.0* 12.56 127.5* 11.86 688.1 10.88 469.5 9.31 6812.9* 6.87 1113.2 6.73 2414.9* 5.95 1215.7 5.64 4916.3 5.44 919.0 4.67 919.7* 4.50 2920.4 4.36 6621.1** 4.21 3721.2 4.19 3422.4* 3.96 4122.8 3.91 2923.2 3.83 10024.8** 3.59 1025.9* 3.443 2326.5 3.365 3228.2 3.163 928.7 3.113 2529.5 3.024 829.9* 2.985 1531.5 2.838 832.7 2.739 234.2 2.622 236.4 2.468 237.6 2.392 2______________________________________ *peak may be an impurity **impurity peak
(b) A portion of the as-synthesized CoMnAPSO-11 of example 4G was calcined in air at 600.degree. C. for one (1) hour. The calcined product was characterized by the following X-ray powder diffraction pattern:
______________________________________2.theta. d(.ANG.) (I/Io) .times. 100______________________________________7.5* 11.86 958.2 10.85 689.6 9.19 9513.1* 6.77 4515.9 5.58 9119.8* 4.48 3220.3 4.37 4921.3* 4.17 3422.5** 3.96 6223.4 3.80 10026.0* 3.423 4326.4 3.376 4026.6 3.346 1629.1* 3.073 2729.2 3.061 2830.2* 2.962 2132.8 2.732 2132.9 2.719 3134.7* 2.586 2836.2 2.481 2______________________________________ *peak may contain impurity **impurity peak
(c) The species CoMnAPSO-11 is a molecular sieve having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table IV-G as follows:
TABLE IV-G______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________9.5-9.6 9.31-9.21 m-vs15.7-15.9 5.64-5.57 m-vs20.3-20.4 4.37-4.36 m21.1-21.2 4.21-4.19 m22.1-22.5 4.02-3.95 m23.2-23.4 3.83-3.80 vs______________________________________
(d) All of the CoMnAPSO-11 compositions both as-synthesized and calcined, for which x-ray powder diffraction data have presently been obtained have patterns which are within the generalized pattern of Table V-G, below:
TABLE V-G______________________________________2.theta. d, (.ANG.) (I/Io) .times. 100______________________________________8.1-8.2 10.88-10.85 46-489.5-9.6 9.31-9.19 68-9513.1-13.2 6.77-6.73 24-4515.7-15.9 5.64-5.58 49-9116.3 5.44 919.0 4.67 9-1020.3-20.4 4.37-4.36 49-6621.1-21.2 4.21-4.19 30-3722.1-22.5 4.02-3.96 31-6222.7-22.8 3.92-3.91 28-2923.2-23.4 3.83-3.80 10024.7-24.8 3.60-3.59 10-1426.4-26.6 3.376-3.346 16-4028.1-28.2 3.175-3.163 928.7 3.113 25-2629.2-29.5 3.061-3.024 8-2831.5 2.838 832.7-32.8 2.739-2.732 2-2732.9 2.719 3134.2 2.622 2-1136.2-36.4 2.481-2.468 2-937.6-37.9 2.392-2.374 2-3______________________________________
EXAMPLE 10G
(a) The CoMnAPSO-34, prepared in example 1G, was subjected to x-ray analysis. The CoMnAPSO-34 was impure but was the major phase and was determined to have an x-ray powder diffraction pattern characterized by the following data:
______________________________________2.theta. d(.ANG.) (I/Io) .times. 100______________________________________7.5* 11.84 679.5 9.29 10012.9** 6.89 1114.1 6.29 714.9* 5.93 1416.0 5.54 2218.0 4.93 1019.8* 4.49 1920.6 4.32 5121.1** 4.22 4022.4* 3.96 2825.2 3.530 1229.1* 3.071 629.5 3.024 330.1* 2.968 1030.5 2.928 1631.3 2.862 1133.7 2.659 334.5* 2.601 434.6 2.591 537.8* 2.383 647.7** 1.905 348.9 1.863 249.9 1.828 250.9 1.794 255.8* 1.647 2______________________________________ *peak may contain impurity **impurity peak
(b) A portion of the as-synthesized CoMnAPSO-34 of 2G was calcined in air at 600.degree. C. for one (1) hour. The calcined product was characterized by the following x-ray powder diffraction pattern:
______________________________________2.theta. d(.ANG.) (I/Io) .times. 100______________________________________ 7.5* 11.84 32 9.6 9.20 100 13.0** 6.81 20 14.9* 5.93 416.2 5.48 818.0 4.93 619.3 4.60 3 19.8* 4.49 8 20.9** 4.26 22 21.2** 4.20 2621.5 4.13 3 22.5* 3.96 3223.4 3.81 325.3 3.520 7 26.1* 3.420 1126.2 3.396 728.5 3.129 3 29.2* 3.063 6 30.2* 2.965 631.0 2.881 1131.5 2.840 7 34.7* 2.584 4 34.9* 2.568 338.0 2.368 2______________________________________ *peak may contain impurity **impurity peak
(c) The species CoMnAPSO-34 is a molecular sieve having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VI-G as follows:
TABLE VI-G______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________9.5-9.6 9.29-9.20 vs12.8-13.0 6.92-6.81 w-m16.0-16.2 5.54-5.48 vw-m20.6-20.9 4.32-4.26 m21.1-21.2 4.22-4.20 m25.2-25.3 3.530-3.520 vw-w31.0-31.5 2.881-2.840 w______________________________________
(d) All of the CoMnAPSO-34 compositions, both as-synthesized and calcined, for which x-ray powder diffraction data have been obtainehave patterns which are within the generalized pattern below:
TABLE VII-G______________________________________2.theta. d(.ANG.) (I/Io) .times. 100______________________________________9.5-9.6 9.29-9.20 10012.8-13.0 6.92-6.81 11-2014.1 6.29 7-916.0-16.2 5.54-5.48 8-2318.0 4.93 6-1219.3 4.60 320.6-20.9 4.32-4.26 22-5721.1-21.2 4.22-4.20 26-4021.5 4.13 323.0-23.4 3.87-3.81 2-325.2-25.3 3.530-3.520 7-1425.8-26.2 3.453-3.396 7-1327.5 3.243 228.3-28.5 3.153-3.129 3-429.5 3.024 330.5 2.928 16-1831.0-31.5 2.881-2.840 11-1333.7-33.8 2.659-2.652 2-734.5-34.6 2.601-2.592 538.0 2.368 239.6 2.276 243.3 2.090 247.5-47.7 1.914-1.905 2-348.9-49.0 1.863-1.859 2-449.9 1.828 250.8-50.9 1.797-1.794 2-3______________________________________
EXAMPLE 15G
In order to demonstrate the catalytic activity of the CoMnAPSO compositions, calcined samples of the products of examples 2G and 4G, were tested for catalytic cracking. The CoMnAPSO compositions were evaluated for n-butane cracking using a bench-scale apparatus.
The reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm I.D. In each test the reactor was loaded with particles of the CoMnAPSO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The CoMnAPSO samples had been previously calcined in air to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500.degree. C. for one hour. The feedstock was a helium-n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation.
The pseudo-first-order rate constant (k.sub.A) was calculated to determine the relative catalytic activity of each CoMnAPSO composition. The k.sub.A value (cm.sup.3 /g min) obtained for the CoMnAPSO are set forth below:
______________________________________Product of Example No. Rate Constant (k.sub.A)**______________________________________2G* 6.94G* 0.8______________________________________ *calcined at 600.degree. C. in air for 1.5 hours prior to activation. **(cm.sup.3 /gram minute)
COBALT-MANGANESE-MAGNESIUM-ALUMINUM-PHOSPHORUS-SILICONE-OXIDE SIEVES
Molecular sieves containing coblat, manganese, magnesium, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents
In the following examples the CoMnMgAPSO compositions were prepared using numerous reagents. The reagents employed and abbreviations employed herein, if any, for such reagents are as follows:
(a) Alipro: aluminum isopropoxide;
(b) LUDOX-LS: LUDOX-LS is the tradename of Du Pont for an aqueous solution of 30 weight percent SiO.sub.2 and 0.1 weight percent Na.sub.2 O;
(c) H.sub.3 PO.sub.4 : aqueous solution which is 85 weight percent phosphoric acid;
(d) MnAc: Manganese acetate, Mn(C.sub.2 H.sub.3 O.sub.2).sub.2.4H.sub.2 O;
(e) CoAc: Cobalt Acetate, Co(C.sub.2 H.sub.3 O.sub.2).sub.2.4H.sub.2 O;
(f) MgAc: Magnesium Acetate Mg(C.sub.2 H.sub.3 O.sub.2).4H.sub.2 O;
(g) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide; and
(h) Pr.sub.2 NH: di-n-propylamine, (C.sub.3 H.sub.7).sub.2 NH.
Preparative Procedures
The following preparative examples were carried out by forming a starting reaction mixture by adding the H.sub.3 PO.sub.4 and one half of the quantity of water. To this mixture the aluminum isoproxide was added. This mixture was then blended until a homogeneous mixture was observed. To this mixture the LUDOX-LS was added and the resulting mixture blended (about 2 minutes) until a homogeneous mixture was observed.
Three additional mixtures were prepared using cobalt acetate, magnesium acetate and manganese acetate using one third of the remainder of the water for each mixture. The four mixtures were then admixed and the resulting mixture blended until a homogeneous mixture was observed. The organic templating agent was then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture was observed, i.e., about 2 to 4 minutes. The mixture was then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature for a time. All digestions were carried out at the autogeneous pressure.
The molar composition for each preparation will be given by the relative moles of the components with H.sub.3 PO.sub.4 be given as P.sub.2 O.sub.5.
EXAMPLES 1H to 4H
CoMnMgAPSO molecular sieves were prepared according to the above identified procedure and the CoMnMgAPSO products determined by X-ray analysis. The results of preparative examples 1H to 4H are set forth in Table I-H. Examples AH, BH and CH of Table I-H did not contain a product identifiable by x-ray analysis.
TABLE I-H__________________________________________________________________________Example.sup.1 Template Temp(.degree.C.) Time(days) CoMnMgAPSO Product(s).sup.2__________________________________________________________________________1H TEAOH 100 7 CoMnMgAPSO-342H TEAOH 150 2 CoMnMgAPSO-34; CoMnMgAPSO-53H TEAOH 150 7 CoMnMgAPSO-34; CoMnMgAPSO-54H Pr.sub.2 NH 200 13 CoMnMgAPSO-11AH TEAOH 100 2 --BH Pr.sub.2 NH 150 3 --CH Pr.sub.2 NH 150 10 --__________________________________________________________________________ .sup.1 Reaction mixture comprised: 1.0 R:0.2 MnO:0.2 CoO:0.2 MgO:0.7 Al.sub.2 O.sub.3 :0.8 P.sub.2 O.sub.5 :0.4 SiO.sub.2 :50H.sub.2 O where "R" is the template. .sup.2 Major species as identified by xray powder diffraction pattern of product, except that when two species are identified the species are listed in the order of their predominance in the product. A "--" indicate no CoMnMgAPSO product was indentified by xray analysis.
EXAMPLE 5H
Portions of the products of examples 3H and 4H were calcined in air at 600.degree. C. for 1.5 hour to remove at least part of the organic templating agent. The adsorption capacities of each calcined sample were measured using a standard McBain-Baker gravimetric adsorption apparatus. The samples were activated in a vacuum (less than about 0.04 torr) at 350.degree. C. prior to measurement. The McBain-Baker data for the CoMnMgAPSO products were:
(a) Example 3H (CoMnMgAPSO-34 and CoMnMgAPSO-5):
______________________________________ Kinetic Pressure Temp. Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed______________________________________Oxygen 3.46 105 -183 6.0Oxygen 3.46 733 -183 8.4Neopentane 6.2 742 23.8 1.4Cyclohexane 6.0 65 23.7 2.6n-hexane 6.0 93 23.4 3.3H.sub.2 O 2.65 4.6 23.4 7.3H.sub.2 O 2.65 19 23.7 12.0______________________________________
(b) Example 4H: (CoMnMgAPSO-11)
______________________________________ Kinetic Pressure Temp Wt. %Adsorbate Diameter, .ANG. (Torr) (.degree.C.) Adsorbed______________________________________Oxygen 3.46 105 -183 2.9Oxygen 3.46 733 -183 3.6Neopentane 6.2 742 23.8 0.5Cyclohexane 6.0 65 23.7 2.1H.sub.2 O 2.65 4.6 23.4 4.1H.sub.2 O 2.65 19 23.7 9.1______________________________________
EXAMPLE 6H
Portions of the products of examples 3H and 4H were subjected to chemical analysis. The chemical analyses were as follows:
(a) Example 3H:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 21.5P.sub.2 O.sub.5 40.3SiO.sub.2 6.5CoO.sup.2 4.58MnO 4.41MgO 2.43Carbon 6.9LOI* 18.3______________________________________ *Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of:
0.575R:0.061CoO:0.062MnO:0.060MgO:0.211Al.sub.2 O.sub.3 :0.284P.sub.2 O.sub.5 :0.108SiO.sub.2
and a formula (anhydrous basis) of:
0.072R(Co.sub.0.048 Mn.sub.0.048 Mg.sub.0.047 Al.sub.0.33 P.sub.0.44 Si.sub.0.084)O.sub.2.
(b) Example 4H:
______________________________________Component Weight Percent______________________________________Al.sub.2 O.sub.3 24.3P.sub.2 O.sub.5 41.8SiO.sub.2 8.5CoO 6.0MnO 6.8MgO 2.8Carbon 1.54LOI* 9.3______________________________________ *Loss on Ignition
The above chemical analysis gives an overall product composition in molar oxide ratios (anhydrous basis) of:
0.128R:0.08CoO:0.096MnO:0.070MgO:0.238Al.sub.2 O.sub.3 :0.294P.sub.2 O.sub.5 :0.141S:O.sub.2
and a formula (anhydrous basis) of:
0.0213R(Co.sub.0.055 Mn.sub.0.066 Mg.sub.0.048 Al.sub.0.33 P.sub.0.41 Si.sub.0.097)O.sub.2.
EXAMPLE 7H
EDAX (energy dispersive analysis by x-ray) microprobe analysis in conjunction with SEM (scanning electron microscope) was carried out on clean crystals of products from examples 3H and 4H. Analysis of crystals having a morphology characteristic of CoMnMgAPSO-5, CoMnMgAPSO-11, and CoMnMgAPSO-34 gave the following analysis based on relative peak heights:
(a) CoMnMgAPSO-5:
______________________________________ Average of Spot Probes______________________________________Co 0.11Mn 0.16Mg 0.08Al 0.55P 1.0Si 0.11______________________________________
(b) CoMnMgAPSO-11:
______________________________________ Average of Spot Probes______________________________________Co 0.09Mn 0.06Mg 0.11Al 0.85P 0.99Si 0.38______________________________________
(c) CoMnMgAPSO-34:
______________________________________ Average of Spot Probes______________________________________Co 0.05Mn 0.03Mg 0.05Al 0.81P 1.0Si 0.20______________________________________
EXAMPLE 8H
(a) CoMnMgAPSO-5, as prepared to in example 3H, was subjected to x-ray analysis and was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.theta. d(.ANG.) 100 .times. I/Io______________________________________7.4 11.89 15 9.5* 9.27 100 12.8** 6.90 1914.1* 6.28 1414.9 5.96 616.0* 5.54 4618.1* 4.90 2819.2* 4.63 1219.7 4.50 1620.6* 4.32 9221.1 4.20 1322.4* 3.97 2222.6 3.94 523.1* 3.85 625.2* 3.529 28 25.8** 3.454 3227.6* 3.237 428.4* 3.142 429.0 3.079 529.5* 3.025 429.9 2.987 7 30.5** 2.930 3731.3* 2.863 2532.4* 2.767 26 34.4** 2.608 1135.4* 2.537 536.3* 2.473 537.8 2.382 438.7* 2.329 638.8* 2.323 639.6* 2.276 543.3* 2.088 545.1 2.010 346.1* 1.971 446.3 1.962 547.2* 1.924 748.7 1.870 648.9* 1.863 651.0* 1.791 453.0* 1.728 453.1* 1.726 4______________________________________ *peak may be an impurity **impurity peak and CoMnMgAPSO5
(b) A portion of the as-sythesized CoMnMgAPSO-5 of part (a) was calcined in air at 600.degree. C. for one (1) hour. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________7.5 11.76 100 9.7* 9.14 86 13.1** 6.79 1815.0 5.90 3016.3* 5.44 818.1* 4.90 719.9 4.47 19 21.2** 4.19 3521.5* 4.13 4422.6 3.94 3723.0* 3.87 626.1 3.414 2126.4* 3.379 929.2 3.060 830.2 2.956 5931.2* 2.871 1231.7* 2.819 734.7 2.582 1335.5* 2.528 16______________________________________ *peak may be an impurity **impurity peak and CoMnMgAPSO5
(c) The species CoMnMgAPSO-5 is a molecular sieve having a three-dimensional microporous framework structure of CoO.sub.2.sup.-2, MnO.sub.-2.sup.-2, MgO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+, and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Co.sub.t Mn.sub.u Mg.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2
wherein "R" represents an organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of Co.sub.t Mn.sub.u Mg.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero to about 0.3; and "t", "u", "v", "x", "y", and "z", where "w" is the sum of "t+u+v", represent the mole fractions of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the tetragonal compositional area defined by points a, b, c, and d of FIG. 2, and having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table II-H:
TABLE II-H______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________7.4-7.5 11.89-11.76 .sup. w-vs14.9-15.0 5.96-5.90 vw-m19.7-19.9 4.50-4.47 w21.1-21.2 4.20-4.19 w-m22.6 3.94 vw-m29.9-30.2 2.987-2.956 vw-m______________________________________
(d) The CoMnMgAPSO-5 compositions for which x-ray powder diffraction data have been obtained have patterns which are characterized by the data of Table III-H below:
TABLE III-H______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________7.4-7.5 11.89-11.76 15-100.012.8-13.1 6.90-6.79 16-1914.9-15.0 5.96-5.90 6-3019.7-19.9 4.50-4.47 16-1921.1-21.2 4.20-4.19 10-3522.6 3.94 5-3725.8-26.1 3.454-3.414 18-3229.0-29.2 3.079-3.060 4-829.9-30.2 2.987-2.956 7-5930.5 2.930 28-3734.4-34.7 2.608-2.582 11-1437.8 2.382 445.1 2.010 346.3 1.962 548.7 1.870 6______________________________________
EXAMPLE 9H
(a) CoMnMgAPSO-11, as prepared in example 4H was subjected to x-ray analysis. CoMnMgAPSO-11 was determined to have a characteristic x-ray powder diffraction pattern which contains the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.1 10.95 219.5 9.35 3413.1 6.75 915.7 5.66 2220.3 4.37 2921.1 4.21 7522.1 4.02 3422.4 3.97 2722.7 3.92 3423.1 3.84 5324.7 3.61 726.4 3.374 2327.6* 3.234 10028.6 3.124 7532.7 2.736 1335.2 2.548 2037.5 2.396 837.8 2.383 937.9 2.373 740.1 2.247 1245.0 2.013 1145.2 2.006 1845.3 2.001 2045.8 1.983 1345.9 1.977 1350.4 1.812 1050.6 1.803 15______________________________________ *peak may contain an impurity
(b) A portion of the as-sythesized of part (a) was calcined in air at 600.degree. C. for one (1) hour. The calcined product was characterized by the x-ray powder diffraction pattern of below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.1 10.95 319.6 9.23 4313.0 6.80 3015.8 5.60 3720.2 4.40 2721.3 4.18 10022.3 3.99 6523.0 3.87 3623.4 3.80 5024.4 3.65 1126.3 3.392 2528.3 3.157 8328.9 3.090 1729.1 3.067 1132.8 2.734 1934.3 2.614 1237.9 2.373 1239.0 2.309 1539.3 2.294 1444.8 2.025 1644.9 2.021 17______________________________________
(c) The species CoMnMgAPSO-11 is a molecular sieve having three-dimensional microporous framework structures of CoO.sub.2.sup.-2, MnO.sub.2.sup.-2, MgO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+, and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula: mR:(Co.sub.t Mn.sub.u Mg.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2 wherein "R" represents an organic templating agent present in the intracrystalline pore system: "m" represents the molar amount of "R" present per mole of (Co.sub.t Mn.sub.u Mg.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero to about 0.3; and "t", "u", "v", "x", "y", and "z", where "w" is the sum of "t+u+v", represent the mole fractions of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being within the compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the compositional area defined by points a, b, c, and d of FIG. 2, and having a characteristic x-ray powder pattern which contains at least the d-spacings set forth in Table IV-H:
TABLE IV-H______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________9.5-9.6 9.35-9.23 m15.7-15.8 5.66-5.60 m21.1-21.4 4.21-4.15 m-vs22.1-22.3 4.02-3.99 m22.7 3.92 m-vs23.3-23.4 3.82-3.80 m28.3-28.7 3.157-3.110 m-s______________________________________
(d) The CoMnMgAPSO-11 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the data of Table V-H below:
TABLE V-H______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________8.1-8.2 10.95-10.65 17-319.5-9.6 9.35-9.23 34-4613.0-13.3 6.80-6.66 9-3015.7-15.8 5.66-5.60 22-3720.2-20.4 4.40-4.35 27-2921.1-21.4 4.21-4.15 75-10022.1-22.3 4.02-3.99 34-6522.4 3.97 2722.7 3.92 34-10023.0-23.2 3.87-3.83 36-5323.3-23.4 3.82-3.80 50-7024.4-24.7 3.65-3.61 7-1126.3-26.5 3.392-3.363 23-2528.3-28.7 3.157-3.110 75-8328.9 3.090 1629.1-30.4 3.067-2.940 11-1432.7-32.8 2.739-2.734 13-1934.3 2.614 1235.2 2.548 2037.5-37.8 2.398-2.383 837.9 2.373 7-1239.0 2.309 1539.3-40.1 2.294-2.247 12-1644.8-45.0 2.025-2.013 11-1745.2 2.006 1845.3 2.001 2045.8 1.983 1345.9 1.977 1350.4 1.812 1050.6 1.803 15______________________________________
EXAMPLE 10H
(a) CoMnMgAPSO-34, as prepared in example 3H, was subjected to x-ray analysis. CoMnMgAPSO-34 was determined to have a characteristic x-ray powder diffraction pattern which contains ao least the d-spacings set forth below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________7.4* 11.89 159.5 9.31 10012.8** 6.90 1914.1 6.28 1414.9* 5.96 616.0 5.54 4618.1 4.90 2819.2 4.62 1219.7* 4.50 1620.6 4.32 9221.1* 4.20 1322.4 3.97 2222.6* 3.94 523.1 3.85 625.2 3.534 2825.8** 3.454 3227.6 3.237 428.4 3.142 429.0* 3.079 529.5 3.025 429.9* 2.987 730.5** 2.930 3731.3 2.863 2532.4 2.767 2634.4** 2.608 1135.4* 2.537 536.3 2.473 537.8* 2.382 438.7* 2.329 638.8 2.323 639.6 2.276 543.3 2.088 545.1* 2.010 346.1* 1.971 446.3* 1.962 547.2 1.924 748.7* 1.870 648.9 1.863 651.0 1.791 453.0 1.728 453.1 1.726 4______________________________________ *peak may contain impurity **peak contains impurity and CoMnMgAPSO34
(b) A portion of the as-synthesized CoMnMgAPSO-34 of part (a) was calcined in air at 600.degree. C. for one (1) hour. The calcined product was characterized by the x-ray powder diffraction pattern below:
______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________7.5* 11.76 1009.7 9.14 8613.1** 6.79 1815.0* 5.90 3016.3 5.44 818.1 4.90 719.9* 4.47 1921.2** 4.19 3521.5 4.13 4422.6* 3.94 3723.0 3.87 626.1** 3.414 2126.4 3.379 929.2* 3.060 830.2* 2.956 5931.2 2.871 1231.7 2.819 734.7* 2.582 1335.5 2.528 16______________________________________ *peak may contain impurity **peak contains impurity and CoMnMgAPSO34
(c) The species CoMnMgAPSO-34 is a molecular sieve having a three-dimensional microporous framework structure of CoO.sub.2.sup.-2, MnO.sub.2.sup.-2, MgO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+, and SiO.sub.2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(Co.sub.t Mn.sub.u Mg.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2
wherein "R" represents an organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of Co.sub.t Mn.sub.u Mg.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero to about 0.3; and "t", "u", "v", "x", "y", and "z", where "w" is the sum of "t+u+v", represent the mole fractions of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being within the compositional area defined by points A, B, C, D and E of FIG. 1, more preferably by the compositional area defined by points a, b, c, and d of FIG. 2, and having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VI-H:
TABLE VI-H______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________9.5-9.7 9.31-9.14 vs16.0-16.3 5.54-5.44 m20.5-21.2 4.33-4.19 m-s21.5 4.13 m25.2 3.534 m30.2-30.5 2.960-2.930 m______________________________________
(d) The CoMnMgAPSO-34 compositions for which x-ray powder diffraction data have been obtained to date have patterns which are characterized by the data of Table VII-H below:
TABLE VII-H______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________9.5-9.7 9.31-9.14 10012.8-13.1 6.90-6.79 13-1914.1 6.28 12-1416.0-16.3 5.54-5.44 31-4618.0-18.1 4.93-4.90 21-2819.2 4.62 5-1220.5-21.2 4.33-4.19 61-9221.5 4.13 4422.4 3.97 4-2523.0-23.1 3.87-3.85 4-625.2 3.534 21-2825.8-26.1 3.453-3.414 13-3226.4 3.379 927.6 3.237 428.4 3.142 4-529.5 3.025 430.2-30.5 2.960-2.930 21-3731.2-31.3 2.871-2.863 14-2531.7 2.819 732.4 2.767 15-2634.4 2.608 5-1135.5 2.528 1636.3 2.473 4-538.8 2.323 639.6 2.276 543.3 2.088 547.2-47.5 1.924-1.916 4-748.9 1.863 4-651.0 1.791 453.0 1.728 453.1 1.726 4______________________________________
EXAMPLE 11H
The catalytic activity of the CoMnMgAPSO compositions of examples 3H and 4H were evaluated in n-butane cracking using a bench-scale apparatus.
The reactor was a cylindrical quartz tube 254 mm. in length an 10.3 mm. I.D. In each test the reactor was loaded with particles of the test CoMnMgAPSO's which were 20-40 mesh (U.S. Std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the conversion of n-butane was at least 5% and not more than 90% under the test conditions. The CoMnMgAPSO samples were calcined in air at 600.degree. C. for 1.5 hours to remove organic materials from the pore system, and were activated in situ in the reactor in a flowing stream of helium at 500.degree. C. for one hour. The feedstock was a helium-n-butane mixture containing 2 mole percent n-butane and was passed through the reactor at a rate of 50 cc./minute. Analysis of the feedstock and the reactor effluent were carried out using conventional gas chromatography techniques. The reactor effluent was analyzed after 10 minutes of on-stream operation. From the analytical data the pseudo-first-order rate constants (k.sub. A) were calculated and are set forth in Table VIII-H below:
TABLE VIII-H______________________________________Product of Ex. No.: Rate Constant (k.sub.A)**______________________________________3H* 8.84H* 0.2______________________________________ *calcined at 600.degree. C. in air for 1.5 hours **(cm.sup.3 /gram minute)
PROCESS APPLICATIONS
The ELAPSO compositions of the instant invention exhibit novel surface selectivity characteristics which render them useful as catalysts or catalyst bases in a number of hydrocarbon conversion and oxidative combustion reactions. They can be impregnated or otherwise loaded with catalytically active metals by methods well known in the art and used, for example, in fabricating catalyst compositions having silica or alumina bases. Of the general class, those species having pores larger than about 4 .ANG. are preferred for catalytic applications.
Among the hydrocarbon conversion reactions catalyzed by ELAPSO compositions are cracking, hydrocracking, alkylation for both the aromatic and isoparaffin types, isomerization including xylene isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydrodecyclization and dehydrocyclization.
Using ELAPSO catalyst compositions which contain a hydrogenation promoter such as platinum or palladium, heavy petroleum residual stocks, cyclic stocks and other hydrocrackable charge stocks, can be hydrocracked at temperatures in the range of 400.degree. F. to 825.degree. F. using molar ratios of hydrogen to hydrocarbon in the range of between 2 and 80, pressures between 10 and 3500 p.s.i.g., and a liquid hourly space velocity (LHSV) of from 0.1 to 20, preferably 1.0 to 10.
The ELAPSO catalyst compositions employed in hydrocracking are also suitable for use in reforming processes in which the hydrocarbon feedstocks contact the catalyst at temperatures of from about 700.degree. F. to 1000.degree. F., hydrogen pressures of from 100 to 500 p.s.i.g., LHSV values in the range of 0.1 to 10 and hydrogen to hydrocarbon molar ratios in the range of 1 to 20, preferably between 4 and 12.
These same catalysts, i.e. those containing hydrogenation promoters, are also useful in hydroisomerizations processes in which feedstocks such as normal paraffins are converted to saturated branched chain isomers. Hydroisomerization is carried out at a temperature of from about 200.degree. F. to 600.degree. F., preferably 300.degree. F. to 550.degree. F. with an LHSV value of from about 0.2 to 1.0. Hydrogen (H) is supplied to the reactor in admixture with the hydrocarbon (Hc) feedstock in molar proportions (H/Hc) of between 1 and 5.
At somewhat higher temperatures, i.e. from about 650.degree. F. to 1000.degree. F., preferably 850.degree. F. to 950.degree. F. and usually at somewhat lower pressures within the range of about 15 to 50 p.s.i.g., the same catalyst compositions are used to hydroisomerize normal paraffins. Preferably the paraffin feedstock comprises normal paraffins having a carbon number range of C.sub.7 -C.sub.20. Contact time between the feedstock and the catalyst is generally relatively short to avoid undesireable side reactions such as olefin polymerization and paraffin cracking. LHSV values in the range of 0.1 to 10, preferably 1.0 to 6.0 are suitable.
The unique crystal structures of the present ELAPSO catalysts and their availability in a form having very low alkali metal content favor their use in the conversion of alkylaromatic compounds, particularly the catalytic disproportionation of toluene, ethylene, trimethyl benzenes, tetramethyl benzenes and the like. In the disproportionation process, isomerization and transalkylation can also occur. Group VIII noble metal adjuvants alone or in conjunction with Group VI-B metals such as tungsten, molybdenum and chromium are preferably included in the catalyst composition in amounts of from about 3 to 15 weight-% of the overall composition. Extraneous hydrogen can, but need not, be present in the reaction zone which is maintained at a temperature of from about 400.degree. to 750.degree. F., pressures in the range of 100 to 2000 p.s.i.g. and LHSV values in the range of 0.1 to 15.
Catalytic cracking processes are preferably carried out with ELAPSO compositions using feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua, etc., with gasoline being the principal desired product. Temperature conditions of 850.degree. to 1100.degree. F., LHSV values of 0.5 to 10 and pressure conditions of from about 0 to 50 p.s.i.g. are suitable.
Dehydrocyclization reactions employing paraffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 carbon atoms, to form benzene, xylenes, toluene and the like are carried out using essentially the same reaction conditions as for catalytic cracking. For these reactions it is preferred to use the ELAPSO catalyst in conjunction with a Group VIII non-noble metal cation such as cobalt and nickel.
In catalytic dealkylation wherein it is desired to cleave paraffinic side chains from aromatic nuclei without substantially hydrogenating the ring structure, relatively high temperatures in the range of about 800.degree.-1000.degree. F. are employed at moderate hydrogen pressures of about 300-1000 p.s.i.g., other conditions being similar to those described above for catalytic hydrocracking. Preferred catalysts are of the same type described above in connection with catalytic dehydrocyclization. Particularly desirable dealkylation reactions contemplated herein include the conversion of methylnaphthalene to naphthalene and toluene and/or xylenes to benzene.
In catalytic hydrofining, the primary objective is to promote the selective hydrodecomposition of organic sulfur and/or nitrogen compounds in the feed, without substantially affecting hydrocarbon molecules therein. For this purpose it is preferred to employ the same general conditions described above for catalytic hydrocracking, and catalysts of the same general nature described in connection with dehydrocyclization operations. Feedstocks include gasoline fractions, kerosenes, jet fuel fractions, diesel fractions, light and heavy gas oils, deasphalted crude oil residua and the like any of which may contain up to about 5 weight-percent of sulfur and up to about 3 weight-percent of nitrogen.
Similar conditions can be employed to effect hydrofining, i.e., denitrogenation and desulfurization, of hydrocarbon feeds containing substantial proportions of organonitrogen and organosulfur compounds. It is generally recognized that the presence of substantial amounts of such constituents markedly inhibits the activity of hydrocracking catalysts. Consequently, it is necessary to operate at more extreme conditions when it is desired to obtain the same degree of hydrocracking conversion per pass on a relatively nitrogenous feed than are required with a feed containing less organonitrogen compounds. Consequently, the conditions under which denitrogenation, desulfurization and/or hydrocracking can be most expeditiously accomplished in any given situation are necessarily determined in view of the characteristics of the feedstocks in particular the concentration of organonitrogen compounds in the feedstock. As a result of the effect of organonitrogen compounds on the hydrocracking activity of these compositions it is not at all unlikely that the conditions most suitable for denitrogenation of a given feedstock having a relatively high organonitrogen content with minimal hydrocracking, e.g., less than 20 volume percent of fresh feed per pass, might be the same as those preferred for hydrocracking another feedstock having a lower concentration of hydrocracking inhibiting constituents e.g., organonitrogen compounds. Consequently, it has become the practice in this art to establish the conditions under which a certain feed is to be contacted on the basis of preliminary screening tests with the specific catalyst and feedstock.
Isomerization reactions are carried out under conditions similar to those described above for reforming, using somewhat more acidic catalysts. Olefins are preferably isomerized at temperatures of 500.degree.-900.degree. F., while paraffins, naphthenes and alkyl aromatics are isomerized at temperatures of 700.degree.-1000.degree. F. Particularly desirable isomerization reactions contemplated herein include the conversion of n-heptene and/or n-octane to isoheptanes, iso-octanes, butane to iso-butane, methylcyclopentane to cyclohexane, meta-xylene and/or ortho-xylene to paraxylene, 1-butene to 2-butene and/or isobutene, n-hexene to isohexene, cyclohexene to methylcyclopentene etc. The preferred form of the catalyst is a combination of the ELAPSO with polyvalent metal compounds (such as sulfides) of metals of Group II-A, Group II-B and rare earth metals. For alkylation and dealkylation processes the ELAPSO compositions having pores of at least 5 .ANG. are preferred. When employed for dealkylation of alkyl aromatics, the temperature is usually at least 350.degree. F. and ranges up to a temperature at which substantial cracking of the feedstock or conversion products occurs, generally up to about 700.degree. F. The temperature is preferably at least 450.degree. F. and not greater than the critical temperature of the compound undergoing dealkylation. Pressure conditions are applied to retain at least the aromatic feed in the liquid state. For alkylation the temperature can be as low as 250.degree. F. but is preferably at least 350.degree. F. In the alkylation of benzene, toluene and xylene, the preferred alkylating agents are olefins such as ethylene and propylene.
As stated the ELAPSO molecular sieves of this invention are useful as adsorbents, i.e., separate mixtures of molecular species. Prior to use in such a separation process, the crystalline materials are activated to remove at least some of any molecular species, e.g., templating agent, which may be present in the intracrystalline pore system as a result of synthesis. This may be accomplished by calcining as generally described above, and more specifically in Examples 109A, 109B, 44C, etc.
The ELAPSO molecular sieves of this invention are capable of separating mixtures of molecular species based on the molecular size (kinetic diameters) or on the degree of polarity of the molecular species. When the separation of molecular species is based on molecular size the crystalline microporous material is chosen in view of the dimensions of its pores such that at least the smallest molecular specie of the mixture can enter the intracrystalline void space while at least the largest specie is excluded.
When the separation is based on degree of polarity, it is generally the case that the hydrophillic ELAPSO molecular sieves of this invention will preferentially adsorb the more polar molecular species of a mixture having different degrees of polarity even though both molecular species can communicate with the pore system of the crystalline material. For example water, which is more polar, will be preferentially adsorbed over common hydrocarbon molecules.

Number	Name	Date
4440871	Lok et al.	Apr 1984
4500651	Lok et al.	Feb 1985
4567029	Wilson et al.	Jan 1986
4683217	Lok et al.	Jul 1987

	Number	Date	Country
Parent	182738	Apr 1988
Parent	600312	Apr 1984

Process for separating molecular species

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