Crystalline manganese phosphate compositions

Abstract

A new family of crystalline manganese phosphate compositions has been prepared. These compositions have an extended network which network can be a one-, two-, or three-dimensional network. The composition has an empirical formula of:(A.sup.a+).sub.v (Mn.sup.b+)(M.sup.c+).sub.x P.sub.y O.sub.zwhere A is a templating agent such as an alkali metal, M is a metal such as Al, Fe.sup.3+ and "b" is the average manganese oxidation state and varies from greater than 3.0 to about 4.0. These compositions can be used as adsorbents and as catalysts in the oxidation of hydrocarbons.

Description

FIELD OF THE INVENTION

This invention relates to a new family of compositions containing at least manganese and phosphate components in an extended network. These compositions can have a one-, two- or three- dimensional network. Further, the average manganese oxidation state varies from greater than 3.0 to about 4.0.

BACKGROUND OF THE INVENTION

Manganese (IV) compounds are well known and are used in a variety of oxidation reactions. For example, manganese dioxide (MnO.sub.2) has been used in the manufacture of chlorine gas from hydrogen chloride and the oxidation of aniline to hydroquinone. See "Chemistry of the Elements", N. N. Woodward and A. Earnnshaw, Pergammon Press, Oxford, pp 1219-20 (1984). A molecular manganese-oxo cluster is involved in the oxidation of water to oxygen in the photosynthesis process used by plants. See Yachandra et.al., Science, 260, 675-679 (1993). Because manganese has stable oxidation states of +4, +3 and +2, manganese oxides can be used in batteries.

Manganese oxides can have layered structures or three-dimensional microporous structures. S. Bach et al., Electrochimica Acta, 36, 1595-1603 (1991), P. LeGoff et al., Mat. Res. Bull., 31, 63-75 (1996), P. Strobel et al., Mat. Res. Bull., 28, 93-100 (1993), Y. Shen et al., Science, 260, 511-515 (1993). Finally, the ion-exchange properties of manganese oxide compositions have been reported by Q. Feng et al. in Chem. Mater., 7, 148-153 and 1722-1727 (1995).

In addition to manganese oxide compounds, there are reports of manganese phosphate molecular complexes containing Mn(IV). For example, Weighardt et al. have reported the synthesis of a trimeric manganese (IV) phosphate complex. Weighardt et al., Chem. Comm., 1145 (1988). A Mn(IV) dimer having the formula �(bpy)(H.sub.2 PO.sub.4)Mn.sup.+4 (.mu.-O).sub.2 (.mu.-HPO.sub.4)Mn.sup.+4 (bpy)!*H.sub.2 O where bpy=bipyridine has been reported by J. Sarneski et al., Inorg. Chem., 30, 2833-35 (1991). M. Jaky has disclosed dilute manganese (IV) phosphate solutions which were used for the oxidation of various organic substrates. Polyhedron, 12, 1271 (1993). Finally, there are a number of examples of Mn(III)-containing phosphates that have been prepared by hydrothermal synthesis, e.g., KMn.sub.2 O(PO.sub.4)(HPO.sub.4), Lightfoot et. al., J. Solid State Chem., 73, 325-329, (1988), and NH.sub.4 Mn.sub.2 O(PO.sub.4)(HPO.sub.4).H.sub.2 O, Lightfoot et. al., J. Solid State Chem., 78, 17-22, (1989).

In contrast to these references, applicant has synthesized crystalline manganese phosphate compounds which contain Mn(IV) and which have an extended network. By extended network is meant that the defining Mn--P--O structural unit of the material repeats itself into at least two adjacent unit cells without termination of bonding, i.e., the material is not molecular. See "Structural Inorganic Chemistry, Fifth Edition," A. F. Wells, Clarendon Press, Oxford, pp. 11-15, (1984). The network can be one-dimensional (a linear chain), two-dimensional (layered) or three-dimensional. The three dimensional network may or may not be a microporous network. There is no mention of a manganese(IV)-containing phosphate material with an extended network. By Mn(IV)-containing phosphate, it is meant that the average oxidation state of Mn is greater than 3.0 but less than or equal to 4.0, indicating the presence of some Mn(IV). These compositions are prepared by employing large excesses of phosphate to avoid the precipitation of insoluble Mn(IV) oxides, and through careful control of the pH and the use of mild reaction conditions. Further, applicant has also synthesized metallo manganese phosphates where a portion of the manganese is replaced by a metal such as iron (III), aluminum, gallium, etc.

SUMMARY OF THE INVENTION

Applicant's invention relates to a crystalline Mn(IV) phosphate composition having an extended network, a process for preparing the composition and processes for using the compositions. Accordingly, one embodiment of the invention is a crystalline manganese phosphate composition having an extended network and an empirical composition on an anhydrous basis expressed by an empirical formula of:

(A.sup.a+).sub.v (Mn.sup.b+)(M.sup.c+).sub.x P.sub.y O.sub.z where A is a templating agent selected from the group consisting of alkali metals, alkaline earth metals, hydronium ion, ammonium ion, organoammonium ions, silver, copper (II), zinc (II), nickel (II), mercury (II), cadmium (II) and mixtures thereof "a" represents a weighted average valence of A and varies from 1.0 to 2.0, "v" is the mole ratio of A to Mn and varies from about 0.1 to about 10.0, "b" is the average valence of Mn and has a value of greater than 3 to about 4, M is a metal selected from the group consisting of Al, Fe.sup.3+, Ga, Sn.sup.4+, Ti, Sb.sup.5+, Ag, Zn, Cu, Ni, Cd, and mixtures thereof "x" is the mole ratio of M to Mn and varies from 0 to about 3.0, "c" is the weighted average valence of M and varies from about 1.0 to about 5.0, "y" is the mole ratio of P to Mn and varies from about 0.10 to about 5.0 and "z" is the mole ratio of O to Mn and has a value determined by the equation z=1/2(a.multidot.v+b+x.multidot.c+5.multidot.y).

Another embodiment of the invention is a process for preparing the manganese phosphate composition described above. This process comprises reacting a mixture containing reactive sources of manganese, phosphorus, M, A and optionally a reductant and a mineralizer at a pH of about 2.0 to about 9.0 and a temperature and time sufficient to form the manganese phosphate composition, the mixture having a composition expressed by:

dAO.sub.a/2 :MnO.sub.m/2 :eMO.sub.c/2 :fP.sub.2 O.sub.5 :gB:hR:tH.sub.2 O where B is a mineralizer, R is a reductant, "d" ranges from about 2.5 to about 20, "e" ranges from 0 to about 3.0, "f" ranges from about 1.0 to about 15, "g" ranges from 0 to about 2, "h" ranges from 0 to about 4, "t" ranges from about 25 to about 1000 and "m" ranges from about 3 to about 7.

Yet another embodiment of this invention is a process for the oxidation of hydrocarbons comprising contacting a hydrocarbon under oxidation conditions with the manganese phosphate described above to give an oxidized product. Further embodiments of this invention involve the use of the manganese phosphate described above in ion exchange application and to separate mixtures of molecular species.

These and other objects and embodiments of the invention will become more apparent after a more detailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION

As stated, the instant invention relates to a crystalline manganese phosphate composition, a process for preparing the composition and processes using the composition. These compositions have an empirical chemical composition on an anhydrous basis expressed by the formula:

(A.sup.a+).sub.v (Mn.sup.b+)(M.sup.c+).sub.x P.sub.y O.sub.z where A is a templating agent selected from the group consisting of alkali metals, alkaline earth metals, hydronium ion, ammonium ion, organoammonium ions, silver, copper (II), zinc (II), nickel (II), mercury (II), cadmium (II), and mixtures thereof "a" represents a weighted average valence of A and varies from 1.0 to 2.0, "v" is the mole ratio of A to Mn and varies from about 0.1 to about 10, "b" is the average valence of Mn and has a value of greater than 3 to about 4, M is a metal selected from the group consisting of Al, Fe.sup.3+, Ga, Sn.sup.4+, Ti, Sb.sup.5+, Ag, Zn, Cu, Ni, Cd, and mixtures thereof, "x" is the mole ratio of M to Mn and varies from 0. to about 3.0, "c" is the weighted average valence of M and varies from about 1.0 to about 5.0, "y" is the mole ratio of P to Mn and varies from about 0.10 to about 5.0 and "z" is the mole ratio of O to Mn and has a value determined by the equation z=1/2(a.multidot.v+b+x.multidot.c+5 y). The alkali metals include lithium, sodium, potassium, rubidium and cesium, while the alkaline earth metals include magnesium, calcium, strontium and barium. Illustrative examples of organoammonium ions include but are not limited to methylaminium, ethylenediaminium, and hexylaminium.

When A is one templating agent, the weighted average valence is the valence of the one templating agent. However, when more than one templating agent is used, the total amount of

A.sub.v.sup.a+ =A.sub.i.sup.a.sbsp.i.sup.+ =A.sub.j.sup.a.sbsp.j.sup.+ =A.sub.k.sup.a.sbsp.k.sup.+ = . . . and the weighted average valance "a" is defined by ##EQU1## The weighted average valence of manganese ("b") is dependent on the amount of Mn.sup.3+ and Mn.sup.4+ present in the composition. Thus, if the total amount of manganese "w" is defined by w=p+q, where "p" is the mole fraction of Mn.sup.3+, "q" is the mole fraction of Mn.sup.4+ then the average valence ##EQU2## Similarly, when two or more metals (M) are present, the amount of each metal is defined by M.sub.x.sup.c+ =M.sub..alpha..sup.c.alpha.+ M.sub.62.sup.c.beta.+ +M.sub..gamma..sup.c.gamma.+ + . . . and the average valence C is determined by the equation ##EQU3##

The crystalline compositions of the invention are characterized in that they have an extended network. By extended network is meant that the defining Mn--P--O structural unit of the material repeats itself into at least two adjacent unit cells without termination of bonding, i.e., the material is not molecular. See "Structural Inorganic Chemistry, Fifth Edition," A. F. Wells, Clarendon Press, Oxford, pp. 11-15, (1984). The compositions can have a one-dimensional network which is a linear chain, a two-dimensional network which is a layered network or a three-dimensional network which is either a microporous framework structure or a non-microporous framework structure.

The instant manganese phosphate compositions are prepared by hydrothermal crystallization of a reaction mixture prepared by combining reactive sources of phosphorus, manganese, optionally one M metal, at least one templating agent plus water. Specific examples of the phosphorus sources which can be used in this invention are orthophosphoric acid, pyrophosphoric acid, alkali phosphates and sodium metaphosphate. The manganese source can be either a high oxidation state salt such as KMnO.sub.4, NaMnO.sub.4, CsMnO.sub.4, NH.sub.4 MnO.sub.4, Mg(MnO.sub.4).sub.2 and Ba(MnO.sub.4).sub.2. Alternatively, the manganese source can be a combination of a high oxidation state manganese salt and a low oxidation state salt which acts as a reductant. The high oxidation state salts can be any of those enumerated above, while the low oxidation state salts include but are not limited to Mn(NO.sub.3).sub.2.6H.sub.2 O, MnSO.sub.4.H.sub.2 O. Manganese oxides such as Na.sub.4 Mn.sub.14 O.sub.27.9H.sub.2 O can also be used. Finally, it is preferred to use a special manganese solution prepared from NaMnO.sub.4 and H.sub.3 PO.sub.4 whose preparation is described in detail in example 1. This phosphate stabilized manganese solution has a composition represented by the empirical formula

NaMnO.sub.4 :rH.sub.3 PO.sub.4 :sR:uH.sub.2 O where R is a reductant selected for the group consisting of H.sub.2 C.sub.2 O.sub.4,Na.sub.2 C.sub.2 O.sub.4, NaHCO.sub.2 and Mn(NO.sub.3).sub.2.6H.sub.2 O, "r" has a value of about 3.0 to about 30, "s" is the mole ratio of R:NaMnO.sub.4 sufficient to reduce the manganese oxidation state from greater than 3 to about 4 and varies from about 1.5 to about 4, and "u" is the moles of water and varies from about 25 to about 1000 in order to vary the manganese concentration from 0.1 wt% to about 5 wt%. The advantage to this solution is that it is stable over a large period of time, i.e., months, and facilitates the preparation of the instant compositions by adding a templating agent to this solution and heating the resultant mixture.

The source of the alkali or alkaline earth metals include the halide, acetate, nitrate, carbonate, and hydroxide salts. Specific examples include sodium chloride, sodium nitrate, sodium acetate, sodium carbonate, sodium hydroxide, lithium chloride, lithium nitrate, lithium carbonate, lithium hydroxide, rubidium chloride, rubidium nitrate, rubidium carbonate, rubidium hydroxide, cesium chloride, cesium nitrate, cesium carbonate, cesium hydroxide, potassium chloride, potassium nitrate, potassium carbonate, potassium hydroxide, magnesium chloride, magnesium nitrate, magnesium carbonate, magnesium hydroxide, calcium chloride, calcium nitrate, calcium hydroxide, calcium carbonate, barium chloride, barium nitrate, barium carbonate, barium hydroxide, strontium chloride, strontium nitrate, strontium carbonate and strontium hydroxide. Sources of organoammonium ions include methylamine, hexylamine, propylamine, and ethylenediamine. The organoammonium cation is generated in situ via protonation. Finally, sources of the M metal include the nitrate salts of the metals as well as TiCl.sub.3, NaSbF.sub.6, and SnCl.sub.4.

Generally, the hydrothermal process used to prepare the manganese phosphate of this invention involves forming a reaction mixture which has the formula:

d AO.sub.a/2 :MnO.sub.m/2 :eMO.sub.c/2 :fP.sub.2 O.sub.5 :gB:hR:tH.sub.2 O where B is a mineralizer, R is a reductant, "d" ranges from about 2.5 to about 20, "e" ranges from 0 to about 3.0, "f" ranges from about 1.0 to about 15, "g" ranges from 0 to about 2, "h" ranges from 0 to about 4, "t" ranges from about 25 to about 1000, and "m" ranges from about 3 to about 7. Examples of the mineralizer B included HF and NaF, while examples of the reductant R include NaHCO.sub.2, H.sub.2 C.sub.2 O.sub.4, and Na.sub.2 C.sub.2 O.sub.4.

It also is necessary to adjust the pH of the mixture to a value of about 2.0 to about 9.0. The pH of the mixture can be controlled by addition of a base such as NaOH, NH.sub.4 OH, amines, etc.

Having formed the reaction mixture, it is next reacted at a temperature of about 50.degree. C. to about 125.degree. C. for a period of about 12 hours to about 96 hours. The reaction is carried out under atmospheric pressure or the reaction vessel may be sealed and the reaction run at autogenous pressure. In a preferred method the phosphorus source is orthophosphoric acid, the manganese source is NaMnO.sub.4 *H.sub.2 O, the temperature is from about 70.degree. C. to about 100.degree. C. and the time required to crystallize the product is from about 16 hours to about 36 hours.

It should be pointed out that not all the enumerated templating agents can provide all the various structures possible in the generic class of extended network manganese phosphate compositions. The relationship of specific templating agent to individual products is apparent from the illustrative examples set forth herein.

The crystalline manganese phosphate compositions of this invention can be used in various oxidation processes. Examples of these processes include conversion of hydrocarbons to alcohols, ethers, aldehydes, ketones or acid anhydrides; conversion of alcohols to aldehydes, ketones or carboxylic acids, conversion of mercaptans to sulfoxides, sulfones or sulfates; conversion of amines to amides and the oxidation of cyanides. The conditions for these processes are known and generally involve contacting a hydrocarbon with the crystalline manganese phosphate compositions of this invention under oxidation condition to give an oxidized product. The oxidation of cyanides is also well documented. The compositions of this invention can also be used as battery electrodes. These compositions can be used as ion exchangers and can purify various waste streams. Finally, those compositions having a three-dimensional network can be used to separate mixtures of molecular species by selective adsorption. Again such processes are well known in the art.

The oxidation state of manganese in the manganese phosphates described here is one of the characterizing properties of these new materials. The measurement of the oxidation state of manganese was carried out according to a variation of the oxalate method given in Piper et. al., Geochimica et Cosmochimica Acta, 48, 1237-1247, (1984). The Mn-containing sample is reduced to Mn.sup.2+ when it is digested at 85.degree. C. in a dilute sulfric acid solution containing a known excess of sodium oxalate, the reducing agent. The solution is divided into two portions, one of which is analyzed for total Mn. In the second portion, the excess oxalate not consumed by the reduction of the sample is back-titrated with standardized KMnO.sub.4, allowing the determination of the amount of oxalate consumed by the sample. The average oxidation state of manganese is then determined from the amount of oxalate consumed and the concentration of Mn in the sample.

In the examples which follow elemental analyses were conducted on air dried samples. Analysis was carried out for all elements except oxygen. Organic ammonium salts were determined by high temperature oxidative pyrolysis, yielding C, H, and N analyses. Because of the oxidizing nature of the reaction mixture used to prepare the compositions of this invention, all the metals (other than Mn) were assumed to be in their highest oxidation state, e.g., Fe.sup.3+ or Ti.sup.4+. Therefore, the oxygen stoichiometry was determined from the known oxygen requirements of all of the elements including the measured oxidation state of the manganese.

The structure of the manganese phosphates of this invention was determined by x-ray analysis. The x-ray patterns were obtained 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.theta. (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 a Siemens D-500 x-ray powder diffractometer, Siemens Type K-805 x-ray sources, available from Siemens Corporation, Cherry Hill, N.J., 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, and w which represent very strong, strong, medium, and weak, respectively. In terms of 100.times.I/I.sub.o, the above designations are defined as

w=0-15; m=15-60; s=60-80 and vs=80-100.

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.

To allow for ready reference, the different structure types in the following examples have been given arbitrary numbers such as NaMnP-1. Thus NaMnP-1 and KNaMnP-1 have the same strcuture, i.e., structure type 1. One particular structure is the pharmacosiderite structure which has been designated--P. Additionally, variations have been observed in compositions having the same structure types. These have been designated by a letter after the number, e.g., NaMnP-2a and NaMnP-2b.

In order to more fully illustrate the variety of species to be derived from the instant invention, the following examples are set forth. It is to be understood that the examples are only by way of illustration and are not intended as an undue limitation on the broad scope of the invention as set forth in the appended claims.

EXAMPLE 1

The preparation of the series of manganese phosphates described below was carried out using a stock solution containing 1 wt.% manganese (0.2M) which can be stored for months without appreciable decomposition. This solution is referred to herein as the "1% Solution". The high concentration and stability of the 1% solution makes it a preferred material for preparing the manganese phosphate compositions of this invention.

In a 12 liter round bottom flask equipped with a mechanical stirrer and a dropping funnel there was added 5800 g of distilled water followed by 1802 g of concentrated (85.7 wt.%) H.sub.3 PO.sub.4 and 250 g of NaMnO.sub.4.H.sub.2 O to give a dark purple solution. In a separate container 159.44 g of NaHCO.sub.2 was dissolved in 576 g distilled water. This solution was placed in a dropping funnel and added dropwise to the stirring NaMnO.sub.4 /H.sub.3 PO.sub.4 solution. The resultant mixture became a black-brown color over the course of the addition. Upon completion of the addition, the mixture was stirred for three to five days and then filtered on a buchner funnel. The filtered solution was analyzed and found to contain 1.0.+-.0.1 wt.% Mn and the manganese had an average oxidation state of 3.85. This solution was identified as "1% Solution".

EXAMPLES 2-10

A series of compositions were prepared using the "1% Solution" and the general procedure set forth below. Specific amounts of reagents and specific conditions are presented in Table 1.

GENERAL PREPARATION PROCEDURE

1) In a container there was placed the desired amount of "1% Solution" and to it was added dropwise an aqueous base solution to adjust the pH and the resultant mixture was stirred for 15 minutes to 1 hour.

2) To the mixture there was now added the appropriate amount of templating agent either as a solid or aqueous solution and the mixture stirred for 45 minutes to 2 hours.

3) The resulting mixture of step (2) was placed in a Teflon.RTM. bottle or Teflon.RTM.-lined autoclave and digested for a particular amount of time at a temperature of about 25.degree. C. to about 150.degree. C. at autogenous pressure.

4) The resultant solid product was recovered by filtration and washed with distilled water. The product was dried at room temperature before being submitted for various analyses.

TABLE 1__________________________________________________________________________Synthesis Variables for Examples 2-10.EX. Name 1% Solution (g) Base (g)/H.sub.2 O (g) Template (g) Digestion (hr/.degree.C.)__________________________________________________________________________ 2 NaMnP-1a 1000 g NaOH (65.5 g)/ same as base 20 hr/98.degree. C. H.sub.2 O (154.47 g) (Stirred in a glass vessel) 3 NaMnP-1b 750 g NaOH (72.61 g)/ same as base 21 hr/100.degree. C. H.sub.2 O (290.43 g) 4 NaKMnP-2a 200 g NaOH (11.93 g)/ 1) Propylamine 80 hr/70.degree. C. H.sub.2 O (47.88 g) (4.30 g) 2) KNO.sub.3 (3.69 g) 5 MeNH.sub.3 MnP-2b 200 g NaOH (13.28 g)/ Methylamine 75 hr/70.degree. C. H.sub.2 O (39.83 g) (40% solution) (7.06 g) 6 C.sub.6 NH.sub.3 MnP-3 271.3 g NaOH (19.72 g)/ Hexylamine (10.0 g) 95 hr/25.degree. C. H.sub.2 O (10.0 g) (in a shaker bath) 7 KMnP--P 500 g KOH (46.47 g)/ KNO.sub.3 (7.43 g) 16 hr/100.degree. C. H.sub.2 O (139.41 g) 8 NH.sub.4 MnP--P 500 g NH.sub.4 OH (29.3% NH.sub.4 NO.sub.3 (5.82 g) 16 hr/100.degree. C. NH.sub.3, 46.37 g) 9 RbMnP--P 748 g NaOH (50.0 g)/ RbNO.sub.3 (30.32 g) 23 hr/100.degree. C. H.sub.2 O (50.0 g)10 CsMnP--P 500 g NaOH (28.64 g)/ CsNO.sub.3 (35.48 g) 24 hr/100.degree. C. H.sub.2 O (28.61 g)__________________________________________________________________________

EXAMPLES 11-14

These examples present the synthesis of compositions containing M metals. The procedure used is the same as in Examples 2-10 except that the desired M metal is introduced by mixing an aqueous solution containing the desired M metal with the "1% Solution" and ageing the solution prior to adjustment of the pH. Each of Examples 11-14 used 500 g of the "1% Solution".

TABLE 2______________________________________Synthesis Variables for Examples 12-15 M Solu- Diges- tion (g)// Base (g)/ Tem- tionEX. Name Aging (hr) H.sub.2 O (g) plate (g) hr/.degree.C.______________________________________12 KAlMnP--P Al(NO.sub.3).sub.3 NaOH KNO.sub.3 23 hr/ *9H.sub.2 O (30.56 g)/ (27.61 g) 100.degree. C. (11.38 g)/H.sub.2 O H.sub.2 O (50.0 g)// 14 hr (60.79 g)13 CsAlMnP--P Al(NO.sub.3).sub.3 NaOH CsNO.sub.3 22 hr/ *9H.sub.2 O (29.69 g)/ (53.22 g) 100.degree. C. (11.38 g)/H.sub.2 O H.sub.2 O 50.0 g)// 15 hr (59.71 g)14 KFeMnP--P Fe(NO.sub.3).sub.3 NaOH KNO.sub.3 25 hr/ *9H.sub.2 O (31.92 g)/ (27.61 g) 100.degree. C. 12.26 g)/H.sub.2 O H.sub.2 O (50.0 g)// 13 hr (64.30 g)15 CsFeMnP--P Fe(NO.sub.3).sub.3 NaOH CsNO.sub.3 24 hr/ *9H.sub.2 O (32.02 g)/ (53.22 g) 100.degree. C. 12.26 g)/H.sub.2 O H.sub.2 O (50.0 g)// 13 hr (64.84 g)______________________________________

EXAMPLE 15

Preparation of CsMnP--P

In a glass beaker there were mixed 202.8 g of distilled water, 30.00 g of CsMnO.sub.4 and 136.23 g concentrated phosphoric acid (85.7 wt.% H.sub.3 PO.sub.4). The resultant suspension was heated to 60.degree. C. to dissolve the CsMnO.sub.4. In a separate container a manganese sulfate solution was prepared by dissolving 30.82 g of MnSO.sub.4.H.sub.2 O in 55 g of distilled water. This solution was placed in a buret and slowly added to the warm CsMnO.sub.4 /H.sub.3 PO.sub.4 solution. After addition of the MnSO.sub.4 solution was complete, the mixture was stirred and aged for one hour at which point 357.1 g of an aqueous solution containing 50% CsOH was added dropwise. At this point, the mixture was removed from the heat source, stirred with a high speed stirrer, transferred to a Teflon.RTM.-lined autoclave and digested at 100.degree. C. for 62 hours at autogenous pressure. The dark brown solid was filtered, washed with distilled water and dried at room temperature.

EXAMPLE 16

Preparation of KFeMnP--P

In a beaker there were mixed 156.3 g of distilled water, 194.54 g concentrated phosphoric acid (85.7% H.sub.3 PO.sub.4) and 40.00 g KMnO.sub.4. In a separate container 34.08 g of Fe(NO.sub.3).sub.3.9H.sub.2 O was dissolved in 124 g of distilled water and the solution was slowly added to the KMnO.sub.4 /H.sub.3 PO.sub.4 mixture. Next, a solution of 31.94 KHCO.sub.2 in 114.7 g distilled water was prepared and added dropwise to the reaction mixture. The resultant mixture was heated to 50.degree. C. and held there for 3 hours with stirring. Next, the pH of the mixture was adjusted by dropwise adding a solution composed of 66.0 g of solid KOH (85%) and 66.0 g of distilled water. This reaction mixture was now stirred for one hour, transferred to a Teflon.RTM.-lined autoclave and digested at 100.degree. C. for 62 hours at autogenous pressure. Finally, the red-brown product was filtered, washed with distilled water and dried at room temperature.

EXAMPLE 17

Preparation of KTiMnP--P

In a baffled flask there were added 648.8 g of concentrated phosphoric acid and 1060 g of distilled water. To this solution 75.00 g of NaMnO.sub.4 H.sub.2 O were added and the resultant mixture vigorously stirred. Next 202.5 g of a 20% TiCl.sub.3 solution was added dropwise. During this addition chlorine gas was released. After the addition of the TiCl.sub.3 solution was complete, the temperature of the reaction mixture was raised to 70.degree. C. and held there for three hours with stirring. Next, 396.8 g of a 50% NaOH solution was added to adjust the pH, followed by the addition of 142.3 g of KNO.sub.3. The reaction mixture was homogenized with a high speed stirrer for 1 hour, placed in a Teflon.RTM.-lined autoclave and digested at 125.degree. C. for 97 hours. A red-brown solid was filtered, washed with distilled water and dried at room temperature.

CHARACTERIZATION OF COMPOSITIONS

Samples from each example above were analyzed by x-ray diffraction analysis. The d(.ANG.) spacings and relative intensities are presented in Table 3. As stated, the compounds designated with a -P have the pharmacosiderite structure while compounds identified with -1a, -1b have similar but not identical structures. Elemental analyses were conducted as set forth above and empirical formulas are presented in Table 4.

TABLE 3__________________________________________________________________________Spacings for Examples 2-18d (.ANG.)__________________________________________________________________________Example 2 Example 3 Example 4 Example 5 Example 6NaMnP-1a NaMnP-1b NaKMnP-2a MeNH.sub.3 MnP-2b C.sub.6 H.sub.13 NH.sub.3 MnP-3d (.ANG.) I d (.ANG.) I d (.ANG.) I d (.ANG.) I d (.ANG.) I__________________________________________________________________________7.41 vs 7.73 vs 11.22 vs 11.08 vs 23.56 vs3.68 s 3.78 m 5.62 m 5.60 m2.44 vs 2.43 m 3.23 m 3.70 w1.39 m 1.42 m 2.79 vs 3.24 w 2.68 m 2.80 m 2.12 w 2.74 w 1.62 m 2.68 w 2.21 w 1.62 w__________________________________________________________________________Example 7 Example 8 Example 9 Example 10 Example 11 Example 12KMnP--P NH.sub.4 MnP--P RbMnP--P CsMnP--P KAlMnP--P CsAlMnP--Pd (.ANG.) I d (.ANG.) I d (.ANG.) I d (.ANG.) I d (.ANG.) I d (.ANG.) I__________________________________________________________________________7.55 vs 7.62 vs 7.64 vs 7.55 m 7.51 vs 7.60 m5.31 w 5.38 w 4.39 m 4.37 m 5.31 w 4.38 m4.34 m 4.39 m 3.80 vs 3.79 vs 4.33 m 3.79 vs3.76 m 3.80 w 3.40 w 3.39 w 3.75 m 3.39 w3.07 m 3.10 m 3.10 m 3.10 m 3.06 m 3.09 m2.66 m 2.69 w 2.69 s 2.69 s 2.65 m 2.68 s2.51 m 2.53 w 2.53 m 2.53 m 2.50 w 2.53 m2.38 m 2.40 w 2.40 m 2.40 m 2.37 m 2.40 m2.27 w 2.29 w 2.29 w 2.29 m 2.26 w 2.28 m2.01 w 2.03 w 2.19 m 2.19 m 2.16 w 2.19 m1.89 w 1.90 w 2.03 m 2.03 m 2.00 w 2.03 w1.83 w 1.84 w 1.84 m 1.84 m 1.87 w 1.84 w1.79 w 1.79 w 1.79 m 1.79 m 1.82 w 1.79 w__________________________________________________________________________Example 13 Example 14 Example 15 Example 16 Example 17KFeMnP--P CsFeMnP--P CsMnP--P KfeMnP--P KMnTiP--Pd (.ANG.) I d (.ANG.) I d (.ANG.) I d (.ANG.) I d (.ANG.) I__________________________________________________________________________7.57 vs 7.67 m 7.66 w 7.56 vs 7.61 vs5.35 w 4.42 m 4.42 m 5.38 w 5.37 w4.37 w 3.83 vs 3.82 vs 4.36 w 4.38 m3.79 m 3.42 w 3.44 w 3.78 m 3.79 m3.09 m 3.13 m 3.12 m 3.09 m 3.09 m2.68 w 2.71 s 2.70 m 2.67 m 2.68 m2.40 m 2.55 m 2.55 w 2.52 m 2.53 m2.29 w 2.42 m 2.42 w 2.40 m 2.40 m2.19 w 2.31 m 2.31 w 2.28 w 2.28 w2.03 w 2.21 m 2.21 w 2.19 w 2.19 w1.90 w 2.04 w 2.04 w 2.02 w 2.02 w1.84 w 1.86 w 1.85 w 1.84 w 1.84 w1.79 w 1.80 w 1.80 w 1.79 w 1.79 w__________________________________________________________________________ TABLE 4______________________________________Empirical Formulas and Mn Oxidation State. Mn OxidationExample State Empirical Formula______________________________________Example 2, 3.89 Na.sub.2.03 Mn.sub.6.00 P.sub.1.00 O.sub.15.18NaMnP-1aExample 3, 3.90 Na.sub.3.27 Mn.sub.8.06 P.sub.1.00 O.sub.19.85NaMnP-1bExample 4, 3.32 Na.sub.3.87 K.sub.1.69 Mn.sub.6.0 P.sub.4.89 O.sub.24. 97NaKMnP-2aExample 5, 3.11 Na.sub.4.40 (CH.sub.3 NH.sub.3).sub.1.14 Mn.sub.6.0 P.sub.5.18 O.sub.25.05MeNH.sub.3 MnP-2bExample 6, 3.15 Na.sub.4.51 (C.sub.6 H.sub.13 NH.sub.3).sub.4.54 Mn.sub.9.00 P.sub.8.01 O.sub.38.73C.sub.6 NH.sub.3 MnP-3Example 7, 3.67 Na.sub.0.07 K.sub.2.37 Mn.sub.4.0 P.sub.2.63 O.sub.15. 14KMnP--PExample 8, 3.51 Na.sub.0.05 (NH.sub.4).sub.1.54 Mn.sub.4.0 P.sub.3.19 O.sub.15.79NH.sub.4 MnP--PExample 9, 3.80 Na.sub.0.31 Rb.sub.2.44 Mn.sub.4.0 P.sub.2.65 O.sub.15.6RbMnP--PExample 10, 3.67 No Analysis, See Example 15CsMnP--PExample 11, 3.75 Na.sub.0.14 K.sub.2.45 Al.sub.1.0 Mn.sub.3.0 P.sub.3.3 1 O.sub.16.70KAlMnP--PExample 12, 3.77 Na.sub.0.05 Cs.sub.2.62 Al.sub.0.96 Mn.sub.3.04 P.sub.3.22 O.sub.16.78CsAlMnP--PExample 13, 3.88 Na.sub.0.29 K.sub.2.l7 Fe.sub.0.96 Mn.sub.3.04 P.sub.3.14 O.sub.16.41KFeMnP--PExample 14, 3.71 Na.sub.0.05 Cs.sub.2.73 Fe.sub.0.98 Mn.sub.3.02 P.sub.3.13 O.sub.16.29CsFeMnP--PExample 15, 3.65 Cs.sub.2.38 Mn.sub.4.00 P.sub.3.26 O.sub.16.64CsMnP--PExample 16, 3.84 K.sub.2.97 Fe.sub.1.00 Mn.sub.3.00 P.sub.3.56 O.sub.17.65KFeMnP--PExample 17, 4.70* Na.sub.0.50 K.sub.2.94 Ti.sub.1.52 Mn.sub.2.48 P.sub.3.90 O.sub.xKTiMnP--P______________________________________ *Ti seems to interfere with oxidation state measurement giving a high result.

Examples 11-14 and 16-17 demonstrate placing M metals into the network of the manganese phosphates, in these particular cases, into the manganese phosphate pharmacosiderite structure. The effect of successful metal substitutions can be seen in the properties of the substituted materials. When heated to a sufficiently high temperature, the manganese phosphate pharmacosiderites undergo an autoreduction via oxygen loss, the characteristic temperature of which is determined by thermogravimetric analysis. The data in Table 5 show that substitution of Mn by Al, Fe, or Ti stabilize the structure to this oxygen loss, shifting the oxygen loss process to higher temperatures.

TABLE 5______________________________________Oxygen Loss Temperatures determined byThermogravimetric AnalysisComposition Temperature of O.sub.2 Loss______________________________________KMnP--P 535.degree. C.KAlMnP--P 560.degree. C.KFeMnP--P 550.degree. C.KTiMnP--P 585.degree. C.______________________________________

EXAMPLE 18

Ion Exchange Determination

In a typical experiment, 5-7.5 g of the material to be exchanged was placed in 500 ml of a metal nitrate solution which is 0.25M with respect to the exchanging cation. The solid was stirred in the exchange solution for 24 hours at 60.degree. C. The products were isolated by filtration and washed thoroughly with distilled water. The solids were characterized by x-ray diffraction and elemental analysis was used to determine the extent of the ion-exchange. The results are reported in terms of the percentage of the exchange sites occupied by the incoming cations.

TABLE 6______________________________________Ion-exchange results for KMnP--P and NaMnPa-1Exchange Cation % Exchange KMnP--P % Exchange NaMnPa--1______________________________________Cs.sup.+ 91% exchanged 94.2% exchangedNH.sub.4.sup.+ 75% exchanged 97.5% exchangedK.sup.+ 95.0% exchangedSr.sup.2+ 55% exchanged______________________________________

EXAMPLE 19

Adsorption measurements were performed using a standard McBain-Bakr gravimetric adsorption apparatus on the following samples. The samples were activated at 200.degree. C. overnight under vacuum to remove adsorbed water from the pores. The samples were then exposed to the various partial pressures of the gases as indicated in tables 7-9. The adsorption of the gases is expressed in terms of the weight percent of the sample. The molecular sieve effect is demonstrated for both the K.sup.+ and Cs.sup.+ forms of materials of the same framework composition. The Cs.sup.+ forms are about 1.5 times heavier on a molar basis than the K.sup.+ forms. The K.sup.+ and Cs.sup.+ are located in the pores of the pharmacosiderite structure and can affect adsorption properties of the different molecules in the pores. It is shown that the larger Cs.sup.+ interferes more with the adsorption of the molecules than K. The ionic radii of K.sup.+ and Cs.sup.+ are 1.35 .ANG. and 1.67 .ANG. respectively. The kinetic diameters of water, carbon dioxide, and oxygen are 2.65 .ANG., 3.3 .ANG., and 3.46 .ANG. respectively.

TABLE 7______________________________________Adsorption of WaterP/P.sub.0(partial KFeMnP--P KAlMnP--P CsFeMnP--P CsAlMnP--Ppressure) wt. % water wt. % water wt. % water wt. % water______________________________________0.19 9.28% 8.90% 2.69% 3.66%0.42 10.56% 9.36% 2.89% 3.84%0.74 11.69% 10.96% 3.47% 4.49%______________________________________ TABLE 8______________________________________Adsorption of Carbon DioxideP/P.sub.0(Partial KFeMnP--P KAlMnP--P CsFeMnP--P CsAlMnP--Ppressure) wt. % CO.sub.2 wt. % CO.sub.2 wt. % CO.sub.2 wt. % CO.sub.2______________________________________0.13 7.47% 4.68% 1.10% 1.74%0.52 8.37% 5.48% 1.30% 2.11%0.92 8.75% 6.05% 1.50% 2.11%______________________________________ TABLE 9______________________________________Adsorption of OxygenP/P.sub.0(Partial KFeMnP--P KAlMnP--P CsFeMnP--P CsAlMnP--PPressure) wt. % O.sub.2 wt.% O.sub.2 wt. % O.sub.2 wt. % O.sub.2______________________________________0.13 4.07% 1.25% 1.99% 1.65%0.52 4.98% 1.49% 2.99% 2.47%0.92 5.20% 1.60% 3.09% 2.56%______________________________________ These results show the microporosity of these materials and that they have pore diameters of about 3.5 .ANG..

Claims

1. A crystalline manganese phosphate composition having an extended network and an empirical composition on an anhydrous basis expressed by an empirical formula of:

(A.sup.a+).sub.v (Mn.sup.b+)(M.sup.c+).sub.x P.sub.y O.sub.z

where A is a templating agent selected from the group consisting of alkali metals, alkaline earth metals, hydronium ion, ammonium ion, organoammonium ions, silver, copper (II), zinc(II), nickel (II), mercury (II), cadmium (II), and mixtures thereof, "a" represents a weighted average valence of A and varies from 1.0 to 2.0, "v" is the mole ratio of A to Mn and varies from about 0.1 to about 10, "b" is the average valence of Mn and has a value of greater than 3 to about 4, M is a metal selected from the group consisting of Al, Fe.sup.3+, Ga, Sn.sup.4+, Ti, Sb.sup.5+, Ag, Zn, Cu, Ni, Cd, and mixtures thereof, "x" is the mole ratio of M to Mn and varies from 0 to about 3.0, "c" is the weighted average valence of M and varies from about 1.0 to about 5.0, "y" is the mole ratio of P to Mn and varies from about 0.10 to about 5.0 and "z" is the mole ratio of 0 to Mn and has a value determined by the equation

z=1/2(a.multidot.v+b+x.multidot.c+5.multidot.y).

2. The composition of claim 1 characterized in that it has a one-dimensional extended network.

3. The composition of claim 1 characterized in that it has a two-dimensional extended network.

4. The composition of claim 1 characterized in that it has a three-dimensional extended network.

5. The composition of claim 4 characterized in that the three-dimensional extended network is a microporous network.

6. A process for preparing a crystalline manganese phosphate composition having an extended network and an empirical composition on an anhydrous basis expressed by an empirical formula of:

(A.sup.+).sub.v (Mn.sup.b+)(M.sup.c+).sub.x P.sub.y O.sub.z

where A is a templating agent selected from the group consisting of alkali metals, alkaline earth metals, hydronium ion, ammonium ion, organoammonium ions, silver, copper (II), zinc(II), nickel (II), mercury (II), cadmium (II), and mixtures thereof, "a" represents a weighted average valence of A and varies from 1.0 to 2.0, "v" is the mole ratio of A to Mn and varies from about 0.1 to about 10, "b" is the average valence of Mn and has a value of greater than 3 to about 4, M is a metal selected from the group consisting of Al, Fe.sup.3+, Ga, Sn.sup.4+, Ti, Sb.sup.5+, Ag, Zn, Cu, Ni, Cd, and mixtures thereof, "x" is the mole ratio of M to Mn and varies from 0 to about 3.0, "c" is the weighted average valence of M and varies from about 1.0 to about 5.0, y" is the mole ratio of P to Mn and varies from about 0.10 to about 5.0 and "z" is the mole ratio of O to Mn and has a value determined by the equation

z=1/2(a.multidot.v+b+x.multidot.c+5.multidot.y),

the process comprising reacting a mixture containing reactive sources of manganese, phosphorus, A, and optionally at least one M metal, a reductant and a mineralizer, at a pH of about 2.0 to about 9.0 and a temperature and time sufficient to form the composition, the mixture having a composition expressed by:

d AO.sub.a/2 :MnO.sub.m/2 :eMO.sub.c/2 :fP.sub.2 O.sub.5 :gB:hR:tH.sub.2 O

where B is a mineralizer, R is a reductant, "d" ranges from about 2.5 to about 20, "e" ranges from 0 to about 3.0, "f" ranges from about 1.0 to about 15, "g" ranges from 0 to about 2, "h" ranges from 0 to about 4,"t" ranges from about 25 to about 1000 and "m" ranges from about 3.0 to about 7.0.

7. The process of claim 6 where the temperature varies from about 50.degree. C. to about 125.degree. C. and the time varies from about 12 to about 96 hours.

8. The process of claim 6 where the phosphorus source is selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, alkali phosphates and sodium metaphosphate.

9. The process of claim 6 where the manganese source is selected from the group consisting of KMnO.sub.4, NaMnO.sub.4, NH.sub.4 MnO.sub.4, CsMnO.sub.4, Mg(MnO.sub.4).sub.2 and Ba(MnO.sub.4).sub.2.

10. The process of claim 6 where the manganese source is a manganese solution having a composition represented by the empirical formula:

NaMnO.sub.4 :rH.sub.3 PO.sub.4 :sR:uH.sub.2 O

where R is a reductant selected for the group consisting of H.sub.2 C.sub.2 O.sub.4,Na.sub.2 C.sub.2 O.sub.4, NaHCO.sub.2 and Mn(NO.sub.3).sub.2.6H.sub.2 O, "r" has a value of about 3.0 to about 30, "s" is the mole ratio of R:NaMnO.sub.4 sufficient to reduce the manganese oxidation state from greater than 3 to about 4 and varies from about 1.5 to about 4, and "u" is the moles of water and varies from about 25 to about 1000.