Iron-aluminum-phosphorus-silicon-oxide molecular sieves

FIELD OF THE INVENTION
The instant invention relates to a novel class of crystalline microporous iron-aluminum-phosphorus-silicon-oxide molecular sieves, to the method for their preparation, and to their use as adsorbents and catalysts. These molecular sieve compositions are prepared hydrothermally from gels containing reactive compounds of iron, phosphorus, silicon and aluminum and preferably at least one organic templating agent (or "template") which functions in part to determine the course of the crystallization mechanism and hence the structure of the molecular sieve products.
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 pore 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 alumonophosphate 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 frameworks 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, there is described a novel class of silicon-substituted alumonophosphates which are both microporous and crystalline. The materials have a three-dimensional crystal framework of PO.sub.2.sup.+, AlO.sub.2.sup.- and SiO.sub.2 tetrahedral units 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 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 phorphorus, respectively, present as tetrahedral oxides.
In copending and commonly assigned application Ser. No. 514,334, filed July 15, 1983, 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, 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 invention relates to new iron-aluminum-phosphorus-silicon-oxide molecular sieves having three-dimensional microporous crystal framework structures of FeO.sub.2.sup.2- (or FeO.sub.2.sup.-1), AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral 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 perameters 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
A novel class of iron-aluminum-phosphorus-silicon-oxide molecular sieves having use as adsorbents, ion-exchange media, catalysts, etc. are disclosed having three-dimensional microporous crystal framework structures of FeO.sub.2.sup.-2 (for convenience herein any reference to FeO.sub.2.sup.-2 is meant to also denote reference to FeO.sub.2.sup.-1), AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral units and having a unit empirical formula, on an anhydrous basis, of:
mR:(Fe.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 moles of "R" present per mole of (Fe.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero (0) to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of iron, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. The molecular sieves of the present invention are generally employable as catalysts for various hydrocarbon conversion processes, molecular separations and miscellaneous processes. 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.
Since the designation of the molecular sieves as "iron-aluminum-phosphorus-silicon-oxide molecular sieves" is somewhat cumbersome, the "iron-aluminum-phosphorus-silicon-oxide sieves" of this invention will be referred to hereinafter by the shorthand reference "FeAPSO" to identify the various structural species which make up the FeAPSO class. Each species is assigned a number, e.g., "FeAPSO-i", and is identified, for example, as FeAPSO-5, FeAPSO-11 and so forth where "i" is an integer specific to a given class member as its preparation is reported herein. 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 novel class of iron-aluminum-phosphorus-silicon-oxide molecular sieves having a three-dimensional microporous crystal framework structures of FeO.sub.2.sup.-2 (and/or FeO.sub.2.sup.-), AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units and having a unit empirical formula, on an anhydrous basis, of:
mR:(Fe.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 (1)
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.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of from zero (0) to about 0.3; the maximum value of "m" in each case depends upon the molecular dimensions of the templating agent and the available void volume of the pore system of the particular molecular sieve involved; and "w", "x", "y" and "z" represent the mole fractions of iron, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E of the ternary diagram which is FIG. 1 of the drawings and more preferably are within the tetragonal compositional area defined by points a, b, c, and d of the ternary diagram which is FIG. 2 of the drawings. Points A, B, C, D and E of FIG. 1 represent the following values for "w", "x", "y" and "z":
______________________________________Mole FractionPoint x y (z + w)______________________________________A 0.60 0.38 0.02B 0.38 0.60 0.02C 0.01 0.60 0.39D 0.01 0.01 0.98E 0.60 0.01 0.39______________________________________
Points a, b, c and d of FIG. 2 represent the following values for "w", "x", "y" and "z":
______________________________________Mole FractionPoint x y (z + w)______________________________________a 0.55 0.43 0.02b 0.43 0.55 0.02c 0.10 0.55 0.35d 0.55 0.10 0.35______________________________________
The term "unit empirical formula" is used herein according to its common meaning to designate the simplest formula which gives the relative number of moles of iron, aluminum, phosphorus, and silicon which form the FeO.sub.2.sup.-2, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral units of the FeAPSO and which form the molecular framework of the FeAPSO composition(s). The unit empirical formula is given in terms of iron, aluminum, phosphorus and silicon and does not include other compounds, cations or anions which may be present as a result of the preparation or existence of other impurities or materials in the bulk composition not containing the aforementioned tetrahedral unit. The amount of template R is reported as part of the composition when the as-synthesized unit empirical formula is given, and water may also be reported unless such is defined as the anhydrous form.
The unit empirical formula for a FeAPSO may be given on an "as-synthesized" basis or may be given after an "as-synthesized" FeAPSO composition has been subjected to some post treatment process, e.g., calcination. The term "as-synthesized" herein shall be used to refer to the FeAPSO composition(s) formed as a result of the hydrothermal crystallization but before the FeAPSO composition has been subjected to post treatment to remove any volatile components present therein. The actual value of "m" for a post-treated FeAPSO will depend on several factors (including: the particular FeAPSO, template, severity of the post-treatment in terms of its ability to remove the template from the FeAPSO, the proposed application of the FeAPSO composition, and etc.) and the value for "m" can be within the range of values as defined for the as-synthesized FeAPSO compositions, although such is generally less than the as-synthesized FeAPSO unless such post-treatment process adds template to the FeAPSO so treated. A FeAPSO composition which is in the calcined or other post-treatment form generally has an empirical formula represented by formula (1), except that the value "m" in a calcined FeAPSO is generally less than about 0.02. Under sufficiently severe post-treatment conditions, e.g. roasting in air at high temperature for long periods (over 1 hr.), the value of "m" may be zero (0) or, in any event, the template, R is undetectable by normal analytical procedures.
The FeAPSOs of this new class of compositions will exhibit molecular sieving properties similar to zeolitic aluminosilicates and are capable of reversibly absorbing water and other molecular sieves. While it is believed that iron, aluminum, phosphorus and silicon framework constituents are present in tetrahedral coordination with oxygen, i.e. as tetrahedral oxide units, it is theoretically possible that some fraction, probably minor, of these framework constituents are present in coordination with five or six oxygen atoms. It is not, moreover, necessarily the case that all the iron, aluminum, phosphorus and/or silicon of any given synthesized product as part of the framework in the aforementioned types of coordination with oxygen. Some of each constituent may be in some as yet undetermined form and may not be structurally significant.
Since the present FeAPSO compositions are formed from FeO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units which, respectively, have a net charge of -2 (or -1), -1, +1, and zero (0), 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 FeAPSO 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 proton (H.sup.+), a cation of, e.g. Fe.sup.2+ or Fe.sup.3+, a complex cation present in the reaction mixture, or an organic cation derived from the templating agent. Similarly an FeO.sub.2.sup.- or FeO.sub.2.sup.-2 tetrahedron can be balanced electrically by association with PO.sub.2.sup.+ tetrahedra, a cation of iron, a proton (H.sup.+), an alkali metal cation, organic cation(s) derived from the templating agent, or othr 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, DC (1971)]
The FeAPSOs of the instant invention are generally synthesized by hydrothermal crystallization from a reaction mixture comprising reactive sources of iron, aluminum, phosphorus and silicon, and preferably one or more organic templating agents. Optionally, alkali or other metal(s) may be present in the reaction mixture and may act as templating agents. The reaction mixture is generally placed in a pressure vessel, preferably lined with an inert plastic material, such as polytetrafluoroethylene, and heated, preferably under the autogeneous pressure, at an effective temperature which is generally between about 50.degree. C., and about 250.degree. C. and preferably between about 100.degree. C. and about 200.degree. C., until crystals of the FeAPSO product are obtained. An effective time for obtaining FeAPSO products is generally a period from several hours to several weeks. Generally the crystallization times are from about 2 hours to about 30 days and typically from about 4 hours to about 20 days being employed to obtain FeAPSO crystals. While not essential to the synthesis of the instant molecular sieves, it has been found that in general stirring or other moderate agitation of the reaction mixture and/or seeding the reaction mixture with seed crystals of either of FeAPSO to be produced, or a topologically similar aluminosilicate, alumonophosphate or molecular sieve composition, facilitates the crystallization procedure. The product is recovered by any convenient method, such as centrifugation or filtration.
After crystallization the FeAPSO may be isolated and washed with water and dried in air. As a result of the hydrothermal crystallization, the as-synthesized FeAPSO generally contains within its intracrystalline pore system at least one form of the template employed in its formation. Generally, the template is a molecular species, but it is possible, steric considerations permitting, that at least some of the template is present as a charge-balancing cation. Generally the template is too large to move freely through the intracrystalline pore system of the formed FeAPSO and may be removed by a post-treatment process, such as by calcining the particular FeAPSO at temperatures of between about 200.degree. C. and to about 700.degree. C. so as to thermally degrade the template or by employing some other post-treatment process for removal of at least part of the template from the FeAPSO. In some instances the pores of the FeAPSO are sufficiently large to permit transport of the template, and, accordingly, complete or partial removal thereof can be accomplished by conventional desorption procedures such as carried out in the case of zeolites.
The FeAPSO compositions are generally formed from a reaction mixture containing reactive sources of iron, aluminum, phosphorus and silicon, and preferably an organic templating agent, said reaction mixture comprising a composition expressed in terms of molar oxide ratios of:
eR:(Fe.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :f H.sub.2 O
wherein "R" is an organic templating agent; "e" has a value of from zero to about 6 and is preferably an effective amount greater than zero to about 6; "f" has a value of from about zero to 500, preferably from about 2 to about 300; and "w", "x", "y" and "z" represent the mole fractions, respectively, of iron, aluminum, phosphorus and silicon in the (Fe.sub.w Al.sub.x P.sub.y Si.sub.z) constituent, and each has a value of at least 0.01. In a preferred embodiment the reaction mixture is selected such that the mole fractions "w", "x", "y" and "z" are generally defined as being within the pentagonal compositional area defined by points F, G, H, I and J of the ternary diagram of FIG. 3. Points F, G, H, I and J of FIG. 3 have the following values for "w", "x", "y" and "z":
______________________________________Mole FractionPoint x y (z + w)______________________________________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______________________________________
For reasons unknown at present, not every reaction mixture gives crystalline FeAPSO products when reaction products were examined for FeAPSO products by X-ray analysis. Those reaction mixtures from which crystalline FeAPSO products were obtained are reported in the examples hereinafter as numbered examples and those reaction mixtures from which FeAPSO products were not identified by use of X-ray analysis are reported as lettered examples.
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "w", "x", "y" and "z" such that (w+x+y+z)=1.00 mole, whereas in the examples the reaction mixtures are expressed in terms of molar oxide ratios which may be 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 iron, aluminum, phosphorus and silicon which results in normalized mole fractions based on total moles of the aforementioned components.
The reaction mixture from which the FeAPSOs are formed preferably contains one or more organic templating agents (templates) which can be most any of those heretofore proposed for use in the synthesis of aluminosilicates and aluminophosphates. The template preferably contains at least one element of Group VA of the Periodic Table, particularly nitrogen, phosphorus, arsenic and/or antimony, more preferably nitrogen or phosphorus and most preferably nitrogen and are of the formula R.sub.4 X.sup.+ wherein X is selected from the group consisting of nitrogen, phosphorus, arsenic and/or antimony and R may be hydrogen, alkyl, aryl, araalkyl, or alkylaryl group and is preferably aryl or alkyl containing between 1 and 8 carbon atoms, although more than eight carbon atoms may be present in each "R" group of the template. Templates which are preferred include amines, quaternary phosphonium compounds, and quaternary ammonium compounds, the latter two being represented generally by the formula R'.sub.4 X.sup.+ wherein "X" is nitrogen or phosphorus and each R' is an alkyl, aryl, alkylaryl, or araalkyl group; wherein R' preferably contains from 1 to 8 carbon atoms or higher when R' is alkyl and greater than 6 carbon atoms when R' is otherwise, as hereinbefore discussed. 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 may also be employed. The mono-, di- and tri-amines, including mixed amines, may also be employed as templates either alone or in combination with a quaternary ammonium compound or another template. The exact relationship of various templates when concurrently employed in not clearly understood. Mixtures of two or more templating agents can produce either mixtures of FeAPSOs or in the instance where one template is more strongly directing than another template the more strongly directing template may control the source of the hydrothermal crystallization wherein with the other template serving primarily to establish the pH conditions of the reaction mixture.
Representative templates include: tetramethylammonium; tetraethylammonium; tetrapropylammonium; tetrabutylammonium ions; tetrapentylammonium ions; di-n-propylamine; tripropylamine; triethylamine; triethanolamine; pypyrrolidine; cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylamine; N,N-diethylethanolamine; dicyclohexylamine; N,N-dimethylethanolamine; 1,4-diazabicyclo(2,2,2)octane; N-methyldiethanolamine, N-methyl-ethanolamine; N-methylcyclohexylamine; 3-methyl-pyridine; 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. As will be readily apparent from the illustrative examples set forth hereinafter, not every template will produce every FeAPSO composition although a single template can, with proper selection of the reaction conditions, cause the formation of different FeAPSO compositions, and a given FeAPSO composition can be produced using different templates.
In those instances where an alkoxide is the reactive iron, aluminum, phosphorus or silicon source, the corresponding alcohol is necessarily present in the reaction mixture since it is a hydrolysis product of the alkoxide. It has not as yet been determined whether this alcohol participates in the synthesis process as a templating agent, or in some other function and, accordingly, is not reported as a template in the unit formula of the FeAPSOs, although such may be acting as templates.
Alkali or other metal cations if present in the reaction mixture may facilitate the crystallization of certain FeAPSO species, although the exact function of such cations, when present, in crystallization, if any, is not presently known. Alkali cations present in the reaction mixture generally appear in the formed FeAPSO composition, either as occluded (extraneous) cations and/or as structural cations balancing net negative charges at various sites in the crystal lattice. It should be understood that although the unit formula for the FeAPSOs does not specifically recite the presence of alkali cations they are not excluded in the same sense that hydrogen cations and/or hydroxyl groups are not specifically provided for in the traditional formulae for zeolitic aluminosilicates.
Most any reactive iron source may be employed herein which permits the formation in situ of reactive iron (II) and/or iron (III) ions. The preferred reactive iron sources include iron salts, oxides, hydroxides, sulfate, acetate, nitrate and the like. Other sources such as freshly precipitated iron oxide, .gamma.-FeOOH, are also suitable.
Most any reactive phosphorus source may be employed. Phosphoric acid is the most suitable phosphorus source employed to date. Accordingly, other acids of phosphorus are generally believed to be suitable phosphorus sources for use herein. 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 tetrabutyl-phosphonium bromide have not, apparently, serve as reactive sources of phosphorus, but these compounds do function as templating agents and may also be capable of being suitable phosphorus sources under proper process conditions (yet to be ascertained). Organic phosphorus compounds, e.g. esters, are believed to be generally suitable since they can generate acids of phosphorus in situ. Conventional phosphorus salts, such as sodium metaphosphate, may be used, at least in part as the phosphorus source, but they are not preferred.
Most any reactive aluminum source may be employed herein. The preferred reactive aluminum sources include aluminum alkoxides, such as aluminum isopropoxide, and pseudoboehmite. 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 zerolite synthesis, such as gibbsite, sodium aluminate and aluminum trichloride, can be employed but is generally not preferred.
Most any reactive silicon source may be employed such that SiO.sub.2 tetrahedral units are formed in situ. The reactive silicon source may be silica in the form of a silica sol or as fumed silica, or other conventional sources of silica used in zeolite synthesis such as a reactive solid amorphous precipitated silica, silica gel, alkoxides of silicon, silicic acid, alkali metal silicates and the like.
The FeAPSO compositions of the present invention may exhibit cation-exchange capacity when analyzed using ion-exchange techniques heretofore employed with zeolite aluminosilicates and have pore diameters which are inhibit in the lattice structure of each species and which are at least about 3 .ANG. in diameter. Ion exchange of FeAPSO 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 FeAPSO 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 FeAPSO compositions will have various degrees of hydrothermal and thermal stability, some being quite remarkable in this regard, and will function as molecular sieve adsorbents, hydrocarbon conversion catalysts or catalyst bases.
In each example a stainless steel reaction vessel is utilized and is lined with an inert plastic material, polytetrafluoroethylene, to avoid contamination of the reaction mixture. In general, the final reaction mixture from which each FeAPSO 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 analysis 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 sanned 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 and Siemens Type K-805 X-ray sources, available from Siemens Corporation, Cherry Hill, NJ, 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. 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 K, wherein said x-ray patterns are for both the as-synthesized and calcined forms unless otherwise noted:
TABLE A______________________________________(FeAPSO-5)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______________________________________
TABLE B______________________________________(FeAPSO-11)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-m 3.850-3.802 m-s______________________________________
TABLE C______________________________________(FeAPSO-16)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______________________________________
TABLE D______________________________________(FeAPSO-20)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 3.667-3.663 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______________________________________
TABLE E______________________________________(FeAPSO-31)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______________________________________
TABLE F______________________________________(FeAPSO-34)2.theta. d(.ANG.) Relative Intensity______________________________________9.35-9.7 9.46-9.12 vs12.7-13.0 6.97-6.81 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______________________________________
TABLE G______________________________________(FeAPSO-35)2.theta. 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______________________________________
TABLE H______________________________________(FeAPSO-36)2.theta. d(.ANG.) Relative Intensity______________________________________7.45-8.0 11.14-11.05 vs8.105-8.3 10.9084-10.65 w-m16.3-16.6 5.44-5.34 w-m 18.9-19.414 4.70-4.5721 w-m20.7-21.0 4.29-4.23 w-m______________________________________
TABLE J______________________________________(FeAPSO-44)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______________________________________
TABLE K______________________________________(FeAPSO-46)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______________________________________
The following examples are provided to further illustrate the invention and are not intended to be limiting thereof:
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 8pseudo-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 : 95 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);
(1) TMAOH: tetramethylammonium hydroxide pentahydrate; and
(m) C-hex; cyclohexylamine.
EXAMPLES 1 TO 16
(a) Examples 1 to 8 were carried out to demonstrate the preparation of FeAPSO-34 and FeAPSO-5. The reaction mixtures were prepared by grinding the aluminum iso-propoxide 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 to the above mixture 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 5 to 8
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), time (see Table I) 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.
(b) Examples 9 to 16 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 was added to this mixture except that in examples 13 to 16 the LUDOX 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. 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 A and B in Table I, did not show FeAPSO products when analyzed by X-ray. Examples A and B followed the same procedure employed for Examples 5 and 6.
TABLE I______________________________________ TimeExample Template Temp (.degree.C.) (hr.) FeAPSO Product.sup.1______________________________________1 TEAOH 150 64 FeAPSO-34; FeAPSO-52 TEAOH 150 158 FeAPSO-34; FeAPSO-53 TEAOH 200 64 FeAPSO-34; FeAPSO-54 TEAOH 200 158 FeAPSO-34; FeAPSO-55 TEAOH 150 40 FeAPSO-34; FeAPSO-56 TEAOH 150 161 FeAPSO-34; FeAPSO-57 Pr.sub.2 NH 150 50 FeAPSO-118 Pr.sub.2 NN 150 168 FeAPSO-119 Pr.sub.2 NH 200 50 FeAPSO-1110 Pr.sub.2 NH 200 168 FeAPSO-1111 Pr.sub.3 N 150 50 FeAPSO-512 Pr.sub.3 N 150 168 FeAPSO-513 Pr.sub.3 N 200 50 FeAPSO-514 Pr.sub.3 N 200 168 FeAPSO-5A TEAOH 100 40 --B 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 15 TO 19
Examples 15 to 19 were carried out according to the general preparative procedure employed for examples 7 to 14 with examples 15 to 18 following the procedure employed for examples 7 to 10 and example 19 following the procedure followed for examples 11 to 14. 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.
The number of moles of each component in the reaction mixtures for examples 15 to 18 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 19 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.
TABLE II______________________________________Exam-ple Template Temp (.degree.C.) Time (hr.) FeAPSO Product.sup.1______________________________________15 Pr.sub.3 N 150 48 FeAPSO-516 Pr.sub.3 N 150 160 FeAPSO-517 Pr.sub.3 N 200 48 FeAPSO-518 Pr.sub.3 N 200 160 FeAPSO-519 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 20-27
Examples 20-27 were carried out according to the general preparative procedure employed for examples 1 to 8 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 Si0.sub.2 * 0.2, 0.6 FeO** 0.2 Template 1.0 H.sub.2 O 50______________________________________ *0.2 moles in examples 20 to 23 and 0.6 moles in examples 24 to 27 **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.
TABLE III______________________________________Exam- Tem- Tempple plate (.degree.C.) Time (hr.) FeAPSO Product.sup.1______________________________________20 Quin 150 64 FeAPSO-1621 Quin 150 158 FeAPSO-16; FeAPSO-3522 Quin 200 64 FeAPSO-16; FeAPSO-3523 Quin 200 158 FeAPSO-16; FeAPSO-3524 MQuin 100 49 FeAPSO-1625 MQuin 100 161 FeAPSO-1626 MQuin 150 49 FeAPSO-16; FeAPSO-3527 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 28 AND 29
Examples 28 and 29 were carried out according to the procedure of Examples 13 to 16, 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 C and D followed the procedure for Examples 28 and 29. 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.
TABLE IV______________________________________Exam-ple Template Temp (.degree.C.) Time (hr.) FeAPSO Product.sup.1______________________________________28 TBAOH 200 49 FeAPSO-529 TBAOH 200 161 FeAPSO-5C TBAOH 150 49 --D 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 30 TO 43
Examples 30 to 43 were carried out according to the procedure employed for examples 1 to 8 except that in examples 30 and 31 the aluminum source was CATAPAL and in examples 33 to 36 and 43 a seed crystal of a topologically similar molecular sieve was employed. The number of moles of each component in the reaction mixture in examples 30 to 43 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 32 and was 2.0 moles of template in examples 37 to 40.
The template, temperature, time for the crystallization procedure and the observed FeAPSO products are reported in Table V.
TABLE V______________________________________Exam- Temp Timeple Template (.degree.C.) (hr.) FeAPSO Product(s).sup.1______________________________________30 TMAOH 150 42 FeAPSO-2031 TMAOH 150 132 FeAPSO-2032 C-hex 220 114 FeAPSO-5; FeAPSO-4433 Pr.sub.2 NH 150 47 FeAPSO-3134 Pr.sub.2 NH 150 182 FeAPSO-3135 Pr.sub.2 NH 200 47 FeAPSO-3136 Pr.sub.2 NH 200 158 FeAPSO-3137 Pr.sub.2 NH 150 182 FeAPSO-4638 Pr.sub.2 NH 150 182 FeAPSO-4639 Pr.sub.2 NH 150 47 FeAPSO-5; FeAPSO-3440 Pr.sub.2 NH 200 158 FeAPSO-11; FeAPSO-3141 Pr.sub.3 N 150 42 FeAPSO-542 Pr.sub.3 N 150 132 FeAPSO-543 Pr.sub.3 N 150 42 FeAPSO-5E Pr.sub.2 NH 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 44
(a) Samples of FeAPSO products were calcined at 600.degree. C. in air for 2 hours to remove at least part of the orginaic 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 12):
______________________________________ 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 10):
______________________________________ 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 31):
______________________________________ 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 34):
______________________________________ 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 38):
______________________________________ 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 45
Samples of FeAPSO products were subjected to chemical analysis as follows:
(a) The chemical analysis for FeAPSO-5 (example 12) 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 10) 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; 1.0Al.sub.2 O.sub.3 ; 1.06P.sub.2 O.sub.5 ; 0.08SiO.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 31) 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; 1.0Al.sub.2 O.sub.3 ; 1.04P.sub.2 O.sub.5 ; 0.15SiO.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 34) 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; 1.0Al.sub.2 O.sub.3 ; 0.94P.sub.2 O.sub.5 ; 0.08SiO.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 46
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 characteristics of FeAPSO-5, FeAPSO-11. FeAPSO-20, FeAPSO-31, FeAPSO-34 and FeAPSO-46 gave the following analysis based on relative peak heights:
______________________________________(a) FeAPSO-5 (example 12): Average of Spot Probes______________________________________Fe 0.02Al 0.44P 0.52Si 0.02______________________________________
______________________________________(b) FeAPSO-11 (examp1e 10): Average of Spot Probes______________________________________Fe 0.03Al 0.42P 0.52Si 0.03______________________________________
______________________________________(c) FeAPSO-20 (examp1e 31): Average of Spot Probes______________________________________Fe 0.04Al 0.42P 0.49Si 0.05______________________________________
______________________________________(d) FeAPSO-31 (example 34): Average of Spot Probes______________________________________Fe 0.01Al 0.44P 0.48Si 0.06______________________________________
______________________________________(e) FeAPSO-34 (example 3): Average of Spot Probes______________________________________Fe 0.04Al 0.43P 0.45Si 0.07______________________________________
______________________________________(f) FeAPSO-46 (example 38): Average of Spot Probes______________________________________Fe 0.05Al 0.40P 0.43Si 0.12______________________________________
EXAMPLE 47
(a) FeAPSO-5, as prepared in example 12, 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:
TABLE V______________________________________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 below:
TABLE VI______________________________________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, below:
TABLE VII______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________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 48
(a) FeAPSO-11, as prepared in example 10, 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 below:
TABLE VIII______________________________________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, below:
TABLE IX______________________________________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 2.840-2.841 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 49
(a) FeAPSO-16, as prepared in example 21, 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** 5.61 217.25** 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 below:
TABLE X______________________________________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, below:
TABLE XI______________________________________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 50
(a) FeAPSO-20, as prepared to in example 31, 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 5919.85 4.47 4722.25 3.998 424.35 3.654 10028.2 3.164 1631.6 2.831 1234.7 2.584 1637.6 2.394 240.3 2.240 442.85 2.110 547.65 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 10020.05 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 below:
TABLE XII______________________________________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, below:
TABLE XIII______________________________________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 51
(a) FeAPSO-31, as prepared in example 34, 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 10.41 649.45* 9.35 513.0 6.81 114.6 6.07 115.7 5.64 317.05 5.20 618.3 4.85 320.25 4.39 4921.05* 4.22 921.95 4.05 3222.6 3.936 10023.2 3.833 625.1 3.546 425.65 3.474 426.45 3.372 227.9 3.195 1328.7 3.110 129.7 3.008 731.7 2.821 2032.7 2.739 135.15 2.555 936.1 2.489 237.2 2.418 237.65 2.390 238.15 2.358 339.3 2.293 439.6 2.275 340.2 2.244 245.2 2.006 246.65 1.947 348.65 1.871 250.75 1.799 251.65 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 10.26 739.8* 9.04 312.95 6.83 114.9 5.95 516.2 5.46 417.2 5.16 1118.45 4.80 420.4 4.35 5022.15 4.016 4422.75 3.909 10023.45 3.795 325.3 3.521 525.8 3.449 928.1 3.174 1329.9 2.990 1231.1** 2.876 231.9 2.806 3032.7 2.739 235.3 2.542 1036.3 2.475 537.35 2.407 337.85 2.378 238.35 2.346 339.5 2.282 440.35 2.234 344.15 2.052 245.05* 2.013 245.4 1.997 246.85 1.910 547.65 1.909 248.9 1.863 349.3 1.848 250.95 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 below:
TABLE XIV______________________________________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 below:
TABLE XV______________________________________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 52
(a) FeAPSO-34, as prepared in example 3, 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 59.35 9.5 10012.7 7.0 1014.0 6.3 814.8* 5.99 215.9 5.57 3217.9 4.96 719.6* 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 79.6 9.21 10013.0 6.81 1716.2 5.47 916.9 5.25 118.0 4.93 519.3 4.60 519.9* 4.46 220.9 4.25 1722.55 3.943 723.4 3.802 224.2 3.678 225.1 3.548 526.2 3.401 727.2* 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 below:
TABLE XVI______________________________________2.theta. d, (.ANG.) Relative Intensity______________________________________9.35-9.7 9.46-9.12 vs12.7-13.0 6.97-6.81 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 .sup.______________________________________
(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 below:
TABLE XVII______________________________________2.theta. d, (.ANG.) 100 .times. I/Io______________________________________9.35-9.7 9.46-9.12 l0012.7-13.0 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 3.88-3.80 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 .sup. 0-4(sh)30.4-30.6 2.940-2.922 0-2831.0-31.2 2.885-2.867 2(sh)-17 .sup.32.4 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 53
(a) FeAPSO-35, as prepared in example 27, 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 sh11.4** 7.77 5113.5 6.57 916.0 5.55 317.4 5.09 2817.9 4.95 518.65** 4.76 5021.0 4.22 1521.9 4.06 10022.9** 3.885 923.45 3.793 825.1 3.548 326.5** 3.365 2527.15 3.285 728.6 3.118 1628.9* 3.091 (sh)29.7** 3.010 2732.2 2.780 (sh)32.5** 2.754 1334.6 2.591 737.8* 2.381 1044.1** 2.053 348.25* 1.886 851.6 1.774 152.15** 1.754 254.5** 1.684 3______________________________________ *peak may contain impurity **impurity peak
(b) The FeAPSO-35 compositions are generally characterized by the data of Table XVIII below:
TABLE XVIII______________________________________2.theta. 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 .sup. 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, below:
TABLE XIX______________________________________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 54
(a) FeAPSO-44, as prepared in example 32, 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 7014.95** 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 3422.45** 3.963 63123.1 3.850 724.5 3.635 10024.7** 3.604 4026.0* 3.425 19327.15** 3.283 3028.05* 3.180 1929.05** 3.075 11030.1* 2.966 13730.9 2.894 4033.0 2.714 733.65** 2.664 3734.6** 2.591 10535.55 2.525 12837.0** 2.430 2837.65** 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 below:
TABLE XX______________________________________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 below:
TABLE XXI______________________________________2.theta. d, (.ANG.) 100 .times. I/Io*______________________________________9.5 9.31 2812.95 6.83 2116.15 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 5828.05 3.180 630.1 2.966 1130.9 2.894 1233.0 2.714 235.55 2.525 3942.3 2.137 742.55 2.125 543.7 2.072 547.75 1.904 11______________________________________ *peak intensities were low and may effect accuracy
EXAMPLE 55
(a) FeAPSO-46, as prepared in example 38 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 37.75 11.38 10012.45 7.11 213.2 6.70 213.8 6.41 115.0 5.91 115.35 5.77 116.7 5.31 217.3 5.13 <119.9 4.47 120.6 4.31 321.65 4.11 722.9 3.885 424.3 3.660 325.2 3.534 <126.95 3.307 327.85 3.206 228.35 3.147 128.85 3.093 329.95 2.985 130.2 2.959 <130.95 2.889 <131.35 2.855 231.8 2.814 <133.05 2.711 134.4 2.606 136.05 2.490 336.7 2.448 <139.9 2.259 <141.25 2.188 <144.2 2.049 147.85 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 98.0 11.04 10013.6 6.51 415.35 5.76 316.0 5.55 317.15 5.17 321.3 4.17 222.2 4.006 223.45 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 below.
TABLE XXII______________________________________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 below:
TABLE XXIII______________________________________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 2-32l.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 0-1 30.95 2.889 0-131.3-32.0 2.855-2.797 2 31.8-32.05 2.814-2.792 0-1 33.05 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 0-1 41.25 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 56
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:
TABLE XXIV______________________________________FeAPSO ofExample No:.sup.1 Rate Constant (k.sub.A)______________________________________FeAPSO-5 (Ex. 12) 0.5FeAPSO-11 (Ex. 10) 0.7FeAPSO-31 (Ex. 34) 1.3FeAPSO-46 (Ex. 37) 0.9______________________________________ .sup.1 FeAPSO were calcined as follows prior to being activated: (a) FeAPSO5: at 600.degree. C. in air for 2 hours; (b) FeAPSO11: at 600.degree. C. in air for 2.25 hours; (c) FeAPSO31: at 500.degree. C. to 600.degree. C. in air for 2 hours; and (d) FeAPSO46: heated from 100.degree. C. to 600.degree. C. in nitrogen over a 2hour period.
PROCESS APPLICATIONS
The FeAPSO compositions of the present invention are, in general, hydrophilic and adsorb water preferentially over common hydrocarbon molecules such as paraffins, olefins and aromatic species, e.g., benzene, xylenes and cumene. Thus, the FeAPSOs as a class are useful as desiccants in such adsorption separation/purification processes as natural gas drying, cracked gas drying. Water is also preferentially adsorbed over the so-called permanent gases such as carbon dioxide, nitrogen, oxygen and hydrogen. These FeAPSOs are therefore suitably employed in the drying of reformer hydrogen streams and in the drying of oxygen, nitrogen or air prior to liquifaction.
The present FeAPSO compositions also exhibit novel surface selectivity characteristics which render them useful as catalyst 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 FeAPSO 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 FeAPSO 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 FeAPSO 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 a 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 is supplied to the reactor in admixture with the hydrocarbon feedstock in molar proportions (hydrogen to hydrocarbon) 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 undesirable 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 structure of the present FeAPSO catalysts and their availability in a form totally void of 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 FeAPSO 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 FeAPSO catalyst in conjunction with a Group VIII non-noble metal cation such as zinc 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-heptane 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 FeAPSO 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 FeAPSO 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.

Number	Name	Date
4238318	Kouwenhoven	Dec 1980
4440871	Lok et al.	Apr 1984
4498975	Pine et al.	Feb 1985
4512875	Long et al.	Apr 1985
4554143	Messina et al.	Nov 1985
4567029	Wilson et al.	Jan 1986
4683217	Lok et al.	Jul 1987

Number	Date	Country
0054346	Nov 1981	EPX
0055529	Dec 1981	EPX
0055046	Dec 1981	EPX
0059059	Feb 1982	EPX

Iron-aluminum-phosphorus-silicon-oxide molecular sieves

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