WO1989001912A1

WO1989001912A1 - Crystalline aluminumphosphate compositions

Info

Publication number: WO1989001912A1
Application number: PCT/US1988/002910
Authority: WO
Inventors: Mark E. Davis; Juan M. Garces; Carlos H. Saldarriga; Maria Del Consuelo Montes De Correa
Original assignee: The Dow Chemical Company
Priority date: 1987-08-28
Filing date: 1988-08-24
Publication date: 1989-03-09
Also published as: FI891964A0; FI891964A; JPH03505720A; EP0333816A1; IL87606A0; HUT52003A; FI89037B; JPH0574523B2; IL87606A; CN1018624B; RO104858B1; EP0333816A4; CN1036376A; HU208511B; HU885511D0; FI89037C

Abstract

Crystalline aluminumphosphate compositions having three-dimensional microporous crystal framework structures whose chemical composition expressed in terms of mole ratios is Al2O3:1.0U0.2 P2O5 are disclosed. Adsorption data shows that the compositions are useful as molecular sieves, having intracrystalline micropores capable of admitting molecules having kinetic diameters of from 3 to 14 Angstroms. These compositions have an X-ray diffraction pattern characterized by d spacings at less than about 40 degrees two-theta as measured using copper K-alpha radiation that are substantially as shown in Table 1. The compositions can further comprise a structure-directing agent. Preparation is by admixing an aluminum source, a phosphorus source and 10-100 moles of water per mole of Al2O3 to form a precursor mixture, admixing the precursor mixture with the structure-directing agent to form a reaction mixture, and reacting the reaction mixture under conditions such that an aluminumphosphate composition of the given X-ray diffraction pattern is formed. Metal substituted aluminumphosphate compositions having an X-ray pattern with the same characterizing d spacings can also be prepared such that oxides of one or more metals are also incorporated in the oxide lattice. Among the metals suitable for substitution are silicon, magnesium, zinc, tin, zirconium, titanium, cobalt, and mixtures thereof.

Description

CRYSTALLINE ALUMINUMPHOSPHATE COMPOSITIONS

The present invention relates to crystalline aluminumphosphate compositions and in particular to large pore crystalline aluminumphosphate compositions and to a method for their preparation.

Molecular sieves have been well known in the art for many years. In general, these may be of two types: the zeolitic type, which comprises crystalline aluminosilicate molecular sieves, and other molecular sieves which are not of this crystalline alumino¬ silicate composition.

The naturally occurring and synthetic analogues of the zeolites include over a hundred compositions. Zeolites are, by definition, tectosilicates, which means that their framework comprises tridimensional structures made of SiOi_j and AIO^'^ tetrahedra which share vertices with oxygen atoms. The zeolites can be characterized as having porous structures with openings of uniform dimensions; ion-exchange capacity; and the capacity to reversibly adsorb and desorb molecules within the cavities present in the crystals via the pore openings. These pore openings are defined by the linkage of 10^ tetrahedra, wherein T represents either silicon or aluminum atoms.

Zeolites are synthesized in general by _j. hydrothermal methods from reactive components in closed systems. A large inventory of empirical data on synthesis compositions and conditions leading to the formation of given zeolites is available in the literature. Practice has shown that a wide variety of 10 zeolitic products can be obtained from the same starting composition, depending on the raw materials, mixing methods, and crystallization procedures employed.

1_5 Other crystalline molecular sieves, which are not zeolites, are also well-known. A silica polymorph, which exhibits molecular sieve properties but lacks exchangeable cations, is described in U.S. Patent 4,061,712. Crystalline aluminumphosphates with

20 molecular sieve properties representing a new class of adsorbents are described in U.S. Patent 4,310,440. The properties of these aluminumphosphates are somewhat analogous to zeolitic molecular sieves and, therefore,

_2£- these are useful as catalyst bases or catalysts in various chemical reactions. U.S. Patent 4,440,871 and European Patent Application 0146389 describe crystalline silicoaluminumphosphates with molecular sieve, ion-exchange and catalytic properties analogous 30 to zeolites and/or aluminumphosphate molecular sieves.

Molecular sieve, ion-exchange and catalytic properties, akin to those of zeolites, are also found in certain metallosilicates, in which elements such as 35 beryllium, boron, gallium, iron, titanium, and phosphorus are used as substitutes for the silicon or aluminum. These are described in E. Moretti et al., "Zeolite Synthesis in the Presence of Organic Components," Chimica e Industria, 67 (1985) 21-34.

j. However, all of the crystalline materials described above are known to have free apertures ranging from about 2.1 to about 7.4 Angstroms. The maximum apertures appear to be defined by rings of twelve TOj_j tetrahedra. To date, while there have been

10 reports of the synthesis of non-zeolitic molecular sieve compositions having larger apertures, these reports have not been substantiated. For example, U.S. Patent 4,310,440 describes an aluminumphosphate composition referred to as AlPOi_j-8 (see example 62-A of

T5 that patent) which is reported to significantly adsorb perfluorotributyla ine, PFTBA [(C^Fg^N)]. PFTBA is known to have a kinetic diameter of about 10 A. See R.M. Barrer, Zeolites and Clay Minerals (1978) 7. A 0 similar claim is made for the zeolite referred to as AG-4 in British Patent 1,394,163- However, neither of these references provides sufficient data to determine de initively whether the PFTBA molecules are adsorbed in the micropores themselves, in capillary pores 5 between the crystalline particles, or perhaps in impurities that are either crystalline or amorphous.

Other materials reported to have large pores are Z-21 described in U.S. Patent 3,567,372, and 0 zeolite N, similar to Z-21, described in U.S. Patent

3_*414,602. More recently, Russian workers have claimed a large pore zeolite based on X-ray powder diffraction data. (See "Neorganicheskie Materialy," Izvestlya

Akademii Nauk SSSR 17, 6 (June 1981) 1018-1021.) 5 Accordingly, there are now provided crystalline aluminumphosphate compositions having three-dimensional microporous crystal framework structures whose chemical composition expressed in terms of mole ratios of oxides is

and which are further defined as having an X-ray powder

10 diffraction pattern characterized by d spacings at less than about 40 degrees two-theta as measured using copper K-alpha radiation that are substantially as shown in Table 1.

The present invention further provides

15 crystalline aluminumphosphate compositions having three-dimensional microporous crystal framework structures comprising a structure-directing agent, such that the chemical composition expressed in terms of 20 mole ratios is:

xR: AI2O3 1.0+0.2 P2O5;

wherein AI2O3 and P2O5 orm an oxide lattice; R _pj- represents a structure-directing agent; and x>0; the structures being further defined as having an X-ray powder diffraction pattern characterized by d spacings at less than about 40 degrees two-theta as measured using copper K-alpha radiation that are substantially 30 as shown in Table 1.

The present invention also provides a method of preparing these crystalline aluminumphosphate- compositions from a precursor mixture whose chemical 35 composition expressed in terms of mole ratios is A1₂0₃: 1.0+0.2 P₂0₅: 10-100 H₂0,

further comprising 0.02 to 4.0 moles of a structure- directing agent for each mole of AI2O3, comprising the steps of admixing an aluminum source, a phosphorus source, and water to form the precursor mixture, admixing the precursor mixture with the structure- directing agent to form a reaction mixture, and reacting the reaction mixture under conditions such 10 that a crystalline aluminumphosphate composition, characterized by d spacings at less than about 40 degrees two-theta as measured using copper K-alpha radiation that are substantially as shown in Table 1 , is formed. T5

The present invention further provides crystalline metal substituted aluminumphosphate compositions having three-dimensional microporous crystal framework structures comprising a structure-

20 directing agent, such that the chemical composition expressed in terms of mole ratios is

xR: A1₂0₃: 1.0+0.2 P₂0₅: 0.001-0.5 M0_{z 2}: 10-100 H₂0;

25 wherein AI2O3, ?2^5 ^{and MC}^z/2 ^{form n} oxide lattice; R is a structure-directing agent; x>0; M is a metal; z is the oxidation state of M; and M0_z/₂ is at least one metal oxide; the chemical composition further comprising one or more charge-compensating species; the

30 structures being further defined as having an X-ray powder diffraction pattern characterized by d spacings at less than about 40 degrees two-theta as measured using copper K-alpha radiation that are substantially 3 -5- as shown in Table 1. Finally, the present invention provides a method of preparing these crystalline metal substituted aluminumphosphate compositions from a precursor mixture whose chemical composition expressed in terms of mole ratios is

A1₂0₃: 1.0+0.5 P 0₅: 0.001-0.5 M0_{z 2}: 10-100 H₂0,

wherein M is a metal; z is the oxidation state of M; and 0_z 2 is at least one metal oxide; the chemical composition further comprising from one or more charge- compensating species and 0.02 to 4 moles of a structure-directing agent for each mole of AI2O ; comprising the steps of admixing an aluminum source, a phosphorus source, a metal oxide source, and water to form a precursor mixture, admixing the precursor mixture with the structure-directing agent to form a reaction mixture, and reacting the reaction mixture under conditions such that a crystalline metal substituted aluminumphosphate composition, characterized by d spacings at less than about 40 degrees two-theta as measured using copper K-alpha radiation that are substantially as shown in Table 1 , is formed.

Figure 1 shows argon adsorption isotherms for the aluminumphosphates of the present invention, denoted "VPI-5", and for Zeolite X(Na) , which is used therein for comparison. Zeolite X(Na) is described in U.S. Patent 2,882,244.

Figure 2 shows the effective pore diameters in Angstroms for the aluminumphosphates of the present invention, denoted VPI-5, and for Zeolite X(Na) . The compositions of one embodiment of the present invention are synthetic, crystalline aluminumphosphate materials, hereafter denoted as "VPI- 5", which are capable of reversibly adsorbing and desorbing large molecules, such as triisopropylbenzene, in intracrystalline pores. These materials are comprised of three-dimensional microporous crystal framework structures.

These aluminumphosphate materials can be characterized in a number of ways. In general, the basic chemical composition of the molecular sieves as expressed in terms of mole ratios is

these compositions having a crystalline structure defined by the X-ray powder diffraction pattern having d spacings substantially as given in Table 1. The term "substantially" as used here means that the d spacings given in Table 1 are within the allowance for experimental error, and thus allow for differences attributable to variances in equipment and technique. The Table shows the characteristic d-spacings of VPI-5 between about three degrees two-theta and about 40 degrees two-theta as measured using copper K-alpha radiation. "Characteristic" and "characterizing" as used herein refer to those d spacings representing all peaks having intensities relative to the largest peak greater than or equal to about 10. These peaks are shown as having intensities described as "vs" for very strong or "m" for medium. Peaks of lesser Intensity, described as having weak ("w") intensities, are thus excluded from this definition. The d spacings remain substantially the same after VPI-5 samples are heated to at least about 600°C. This heating can take place, for example, under vacuum, in air, or in air/steam mixtures. The experimental X-ray diffraction patterns were obtained in an automated powder diffraction unit using copper K-alpha radiation.

TABLE 1

X-Ray Powder Diffraction Data for As-Synthesized VPI-5

Another characterization of the aluminum¬ phosphates of the present invention, characterized by the d spacings of the X-ray powder diffraction pattern substantially as shown in Table 1 , on the basis of their composition is

wherein R represents a structure-directing agent used in the synthesis of the large pore material, and x denotes the mole ratio value of R to AI2O , wherein x>0. Since the structure-directing agent is a part of the preparation process, as discussed below, its amount in the composition will depend in part on whether it has been subjected to partial desorption or decomposition.

Referring to Figure 1 , argon adsorption isotherms of the VPI-5 aluminum phosphate of this invention and Zeolite X(Na) , described in U.S. Patent 2,882,244, are shown. These results were determined in an 0MNIS0RP* 360 instrument (*0MNIS0RP is a trademark of Omicron Technology Corporation) at liquid argon temperature. Figure 2 shows effective pore diameters for VPI-5 and the Zeolite of U.S. Patent 2,882,244. The adsorption isotherms and the pore size distributions were derived using Horvath-Kawazoe analysis (G. Horvath et al., "Method for the Calculation of Effective Pore Size Distribution in Molecular Sieve Carbon", J. Chem. Eng. of Japan 16, (5) 470-475 (1983)). Zeolite X(Na) is representative of the faujasite structure with pore openings limited by 12-membered ring tetrahedra whose accepted dimension is around 0.8 nm. This dimension is in good agreement with the value shown in Figure 2. It is evident that VPI-5 has pores substantially larger than Zeolite X(Na).

Thus, from the experiments described above, it is inferred that the VPI-5 compositions exhibit a crystalline structure with a pore system such that some of the pore space is large enough to allow the entry of molecules of triisopropylbenzene. Additional pore space is available to smaller molecules.

The metal substituted aluminumphosphates were also characterized via X-ray diffraction. The observed powder patterns show the same characterizing d spacings as those obtained for the unsubstituted VPI-5, as shown in Table 1. These metal substituted aluminumphosphates show similar molar ratios of AI2O3 to P 05« In general these compositions are defined by the following molar ratios:

A1₂0₃: 1.0±0.2 P 0₅: 0.001-0.5 M0_{z 2}: 10-100 H₂0

In this formula M is a metal, z is the oxidation state of M, and M0_z/₂ is at least one metal oxide. For example, the formula showing the molar ratios of the silicoaluminumphosphate compositions is:

A1₂0₃: 1.0±0.2 P₂0₅: 0.001-0.5 Si0₂: 10-100 H₂0

The structure-directing agent is present in the same proportion for the metal substituted aluminumphosphates as for the unsubstituted aluminumphosphate composi¬ tions, and the same choices as to aluminum and phosphorus sources as well as structure directing agents will be applicable. Similarly, the structure- directing agent may or may not remain in the final silicoaluminumphosphate VPI-5 compositions, depending on whether desorption or decomposition has occurred. The chemical composition further comprises one or more species that are charge-compensating for the metal- ' substituted aluminumphosphates species such that the T charges are balanced. These charge-compensating species can be selected from various cations or anions including, for example, sodium, potassium, hydroxides, chlorides, and so forth, as will be known to those skilled in the art.

10

Other elements from sources capable of forming oxides can also be substituted into the basic VPI-5 aluminumphosphate crystal framework structures without significant effect on the X-ray powder diffraction

15 pattern or general oxide lattice structure. These include, for example, substitute metals such as titanium, tin, cobalt, zinc, magnesium, zirconium, and mixtures thereof.

20 The present invention also comprises a method of preparing the VPI-5 compositions described herein. In general, the specified mole ratios of the constituent reactants are significant in attaining a _pc- final crystalline solid adhering to the above characterizing data. To summarize, the crystalline aluminumphosphates of this invention are prepared by admixing an aluminum source, a phosphorus source, a structure-directing agent, and water to form a reaction

30 mixture, and then reacting the reaction mixture under conditions such that a crystalline aluminumphosphate composition characterized by the d spacings substantially as shown in Table 1 is formed.

35 The combining of the components can be done in a variety of ways, such that the described VPI-5 compositions are produced. For example, the aluminum source can be admixed with water, and the phosphorus source can be separately admixed with water. The phosphorus source/water admixture can then preferably be added to the aluminum source/water admixture while stirring to ensure homogeneity. It is also possible to add the aluminum source to the phosphorous source/water admixture, or to add an aluminum source/water admixture to a phosphorus source/water admixture. Other mixing orders can also be employed.

Following the preparation of the thoroughly mixed phosphorus source/aluminum source/water precursor mixture, it is preferable to age the precursor mixture sufficiently for its pH to stabilize. This aging can be done with or without stirring, but it is preferred that stirring is not done during the time required to allow pH stabilization. The aging is preferably done at room temperature for a period of from 1 to 5 hours.

In preparing the metal substituted aluminumphosphates of the present invention, the metal source can, for example, be preferably added to the aluminum source/phosphorous source/water precursor mixture after it has been aged as described above. It is also possible to add the metal source to an aluminum source/water admixture or to a phosphorus source/water admixture prior to combining the admixtures. It is alternatively also possible to add the metal source in stages at various points in the synthesis.

Starting materials for preparing the aluminumphosphate or metal-substituted aluminumphos- phate compositions of the present invention can be selected from a number of possible choices. Possible sources of phosphorus include, for example, elemental phosphorus, orthophosphoric acid (H3PO4), phosphorus oxide, esters of phosphoric acid, and mixtures of these. Of these, orthophosphoric acid is preferred. Preferred aluminum sources include hydrates of aluminum such as boehmite, pseudo-boehmite, gibbsite, bayerite, and mixtures of these. Elemental aluminum, aluminum alkoxides, aluminum oxides, and mixtures of these are among other possible sources. The phosphorus source

10 and the aluminum source, and in the case of the silicoaluminumphosphate VPI-5, also the silicon source should be such that they are capable of forming an oxide of the metal upon incorporation into the

_1£- aluminumphosphate lattice. Preferred silicon sources include fumed silica, aqueous colloidal silica, tetraethylorthosilicate, and other reactive silicas. Other silicon-containing compounds can also be used. In other metal substituted embodiments of the present 0 invention, the acetate dihydrates or tetrahydrates of the metals, e.g., cobalt acetate tetrahydrate, zinc acetate dihydrate, or magnesium acetate tetrahydrate, are preferred, but other metal-containing compounds are also possible sources. The metal can also be supplied 5 as a complex ion, such q,s a metal oxalate, an ethylenediaminetetraacetic acid complex, or the like.

The next step in the synthesis is the addition of the structure directing agent. This is preferably

30 added to the aged precursor mixture. However, it may also be possible to add it at an earlier point in the synthesis. The structure directing agent combined with all of the other starting materials is called the ^r reaction mixture. It is preferable to age this reaction mixture for 1 to 2 hours, again to allow for pH stabilization.

Various effective structure-directing agents _j- are dipropylamine, diisopropylamine, tetrapropyl- ammonium hydroxide, tetrabutylammonium hydroxide, dipentylamine, tripentylamine, tributylamine, alkylammoniu and alkylphosphonium compounds in general, and mixtures of these. Of these,

10 dipropylamine, tetrabutylammonium hydroxide and dipentylamine are preferred, and more preferred is tetrabutylammonium hydroxide. Related molecules may also serve as structure directing agents in the present invention. 15

The proportions of the reactants can be varied within given ranges. Basing proportions on an AI2O3 molar value of 1, the structure directing agent ("R") to Al₂θ3 molar ratio can be preferably 0.02 to 4, more 0 preferably 0.2 to 2, and most preferably 1; the P2O5 to

AI2O3 molar ratio can be preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and most preferably 1; and the water to Al₂θ3 molar ratio can be preferably 10 to 100, 5 more preferably 30 to 70, and most preferably 35 to 55.

When silicon or another metal ("M") is added to produce the metal substituted aluminumphosphate of the present invention, the above ratios are still applied, and in addition the M0_z/₂ to AI2O3 molar ratio can be 0 preferably from 0.001 to 0.5 mole of metal oxide per mole of AI2O3. Within this general preferred range there is a distinction between silicon substitution and substitution of most other metals. Thus, it is more preferred that the ratio to Al₂θ be 0.2 to 0.5 for 5 silicon dioxide, and most preferred that it be 0.3 to

0.4, while it is more preferred that the ratio to Al₂θ^"3 of most other metal oxides be 0.001 to 0.1, and most preferred 0.02.

In an alternate-embodiment of the present invention it is also possible to substitute a polar organic solvent for part of the water. For this purpose an alcohol, such as hexanol, or a ketone or other polar solvent can be employed. In this case it is preferable to dissolve the structure directing agent directly in the solvent prior to incorporating the agent in the oxide admixture.

Once the minimum components of the reaction mixture, i.e., the aluminum source, the phosphorus source, the structure-directing agent, the water and, optionally, the additional metal source, have been combined to form the reaction mixture and this reaction mixture has been^" referably aged until a substantially constant pH is attained, the reaction mixture is reacted under conditions such that a crystalline solid having the X-ray powder diffraction pattern by which VPI-5 compositions are defined is formed. For this, known methods of heating are preferably employed. Autoclaving in bombs lined with TEFLON* (*TEFL0N is a trademark of Du Pont de Nemours, Inc.) is one effective and convenient means of achieving this. Other types of reactors can alternatively be used. The temperature preferably ranges 50°C to 200°C, and 100°C to 150°C is more preferable. The reaction can preferably be carried out under pressure, for example, autogenous pressure, or at atmospheric pressure.

Time of reaction varies, in part depending on the temperature used. Insufficient heating may lead to amorphous products, and excessive heating may result in the formation of amorphous products or undesirable phases A time of 2 hours to 50 hours in conjunction with a temperature of 100°C to 150°C is preferred, depending on the reactants and the composition of the reaction mixture.

Following crystallization, the product is preferably subjected to conventional means of separation and recovery. Separation from the mother liquor is conveniently accomplished by filtration, but centrifugation, settling and decantation, and related methods can also be employed. The subsequent recovery of the crystalline VPI-5 compositions can involve traditional washings with acid solutions such as HC1 or boric acid, organic solvents such as acetone or methanol, salt solutions such as magnesium acetate, or deionized water, as well as drying and/or .thermal treatment steps. These post-synthesis treatments may help to remove the structure directing agent if desired and may also impart certain physical and chemical properties to the final product. The final crystalline aluminumphosphate compositions will exhibit catalytic, adsorbent ion exchange and/or molecular sieve properties, and may be suitable for catalysis of reactions of various organic compounds.

The following examples are given to more fully show various embodiments of the present invention. They are set forth for illustrative purposes only and are not intended to be, nor should they be construed as being, limitative of the scope of the invention in any way. Example 1

-A slurry of 55.0 g of aluminum oxide dihydrate in 150 g of water is added to a solution of 90 g ortho- phosphoric acid (85 percent ^PO ) and 100 g water. The resulting precursor mixture is aged without agitation for 2 hours at room temperature. 186 g of 55 percent tetrabutylammonium hydroxide (TBA) is added to the precursor mixture and the resulting mixture is stirred for 2.5 hours at room temperature. The composition of the reaction mixture is:

The reaction mixture is heated at 145°C for 24 hours in a TEFLON*-lined stainless steel autoclave. The product is removed, washed with water, and dried at room temperature overnight. The resulting X-ray diffraction pattern is characterized by d spacings that are substantially as shown in Table 1.

Example 2

Seven suspensions of aluminum oxide dihydrate are prepared as listed in Table 2. Each slurry is added to a solution of 11.38 g orthophosphoric acid (85 percent H3PO₁J) and 11.0 g water and aged at room temperature 5 hours without stirring. 23.54 g of 55 percent tetrabutylammonium hydroxide (TBA) is added to each precursor mixture with stirring to give the reaction mixture compositions listed in Table 2.

The reaction mixtures are heated at 150°C for 18 hours in TEFLON* lined stainless steel reactors. The white solids are recovered by slurrying the contents of each reactor with deionized water and allowing the solids to settle. The solids are dried at room temperature in air overnight. The X-ray diffraction pattern of the resulting crystalline materials show a pattern characterized by d spacings that are substantially those of VPI-5 as listed in Table 1.

Example 3

About 8.9 g of aqueous orthophosphoric acid (85 percent concentration) is dissolved in about 6.0 g of distilled water. Separately, a slurry is prepared by mixing about 5.3 g of aluminum oxide dihydrate with about 6.0 g of distilled water. The acid solution is then added to the slurry while stirring at room temperature. The resulting precursor mixture is stirred with a magnetic bar for about 20 minutes. Another solution is prepared by combining about 18.3 g of aqueous 55 percent tetrabutylammonium hydroxide (TBA), and about 10.9 g of distilled water. This solution is then added to the precursor mixture while stirring. Stirring is then continued at room temperature in air for about 1.5 hours. At this point the mixture has the following molar ratio composition:

1.0 TBA: A1₂0₃: P₂0₅ 52 H₂0

Aliquots of this gel (each about 25 percent of the total) are put into autoclaves lined with TEFLON* of about 15 ml internal capacity and sealed. The autoclaves are heated at about 150°C for about 44 hours, The resulting product is isolated as described in Example 1 and is characterized as in Table 1.

Example 4

About 11.50 g of orthophosphoric acid (85 percent concentration H3PO4) is dissolved in about 9.8 g water. The solution is stirred for about 5 minutes, and pH is determined to be about 0. This solution is then added to a slurry prepared by stirring 6.875 g of aluminum oxide dihydrate in 20.0 g of water for about 5 minutes. The pH of the slurry prior to admixing it with the acid solution is about 7. The resulting precursor mixture is homogenized, first by hand and then with a magnetic stirrer, and the pH of the reaction mixture is measured over 110 minutes, as shown in Table 3:

To the foregoing precursor mixture about

5.075 g of dipropylamine (DPrA) is added while TABLE 3

10

15. stirring. The resulting white reaction mixture (pH ~ 3.8) is further homogenized for about 82 minutes. The result is a composition which can be expressed in terms of molar oxide ratios as follows:

0 DPrA: A1₂0₃: P2O5: 40 H₂0

This reaction mixture is then transferred to five TEFLON* lined stainless steel autoclaves labeled, respectively, 1, 2, 3, 4, and 5, and heated under 5 autogenous pressure at 142°C for the times specified in Table 4. The pH is measured as to each of the portions and found to be 7.0.

O

5 TABLE 4

Run Time

A white solid is recovered by separately slurrying the contents of each autoclave in deionized water, stirring for several minutes to allow the solid to settle, and discarding the supernatant liquid. This solid is then filtered and dried in an oven at 100°C and is characterized by Table 1.

Example 5

Five solutions of orthophosphoric acid (85 percent concentration) are prepared as shown in Table 5. Each solution is added dropwise to a slurry of aluminum oxide dihydrate and water. The resulting precursor mixture Is heated at the temperature and for the time indicated in Table 5. Dipropylamine, in the amount shown in Table 5, is added dropwise and the resultant reaction mixture is stirred for several minutes.

Each reaction mixture is then heated at the temperatures and times shown in Table 6 in a stainless TEFL0N*-lined autoclave. White solids are recovered by slurrying the contents of each reactor with deionized water and allowing the solids to settle. The solids are then dried at room temperature in air overnight. The X-ray diffraction pattern of each of. the resulting crystalline solids is characterized by d spacings that are substantially as shown in Table 1.

— Denotes no data

The reaction composition of all runs is DPrA: AI2O3 P2O5: 37 H₂0, and is further characterized by Table 1

Example 6

Four solutions of orthophosphoric acid (85 percent H3PO4) and water are prepared using components as shown in Table 7. Each solution is added dropwise to a slurry of aluminum oxide dihydrate and water, also as shown in that table. The resulting precursor mixtures are stirred and pH is measured. Dipentylamine (DPtA) is added dropwise and each of the resulting reaction precursor mixture(s) is again stirred for the time shown.

The reaction mixtures are heated in stainless steel TEFL0N*-lined autoclaves for periods of time, as shown in Table 8. White solids are recovered by slurrying the contents of each reactor with deionized water and allowing the solids to settle, then washing with acetone. The solids are dried at room temperature in air overnight and are characterized by Table 1.

* Denotes precursor mixture ** Denotes reaction mixture

Example 7

About 8.9 g of orthophosphoric acid H3PO4 is dissolved in about 6.0 g of distilled water. Separately, about 5.3 g of aluminum oxide dihydrate is mixed with about 6.0 g of distilled water. The phosphorus-containing mixture is then added to the aluminum-containing mixture, and the resulting precursor mixture is homogenized by stirring with a magnetic bar for about 20 minutes.

About 7.89 g of an aqueous 95 percent dipentyl¬ amine is then added to the homogenous precursor mixture while stirring, followed by about 10.9 g of distilled water. Stirring of the resulting reaction mixture is continued, at room temperature and in air, for an additional 4.5 hours. The reaction mixture has the 5 following molar ratio composition:

DPtA: A1₂0₃: P2O 40 H₂0

Aliquots (each about 25 percent of the total)

10 of the aged mixture are transferred to autoclaves lined with TEFLON* and heated at 150°C under autogenous pressure.

The solid products are then separated from the _,_£. mother liquor by filtration and recovered by slurrying the contents of each autoclave in about 100 ml of distilled water, stirring for several minutes, allowing the solid to settle by gravity, and then discarding the_. supernatant liquid. Then the solid is filtered and 20 dried in air at J00°C for about 30 minutes.

Example 8

Using the same procedure as in previous _2J- examples, solutions of orthophosphoric acid are prepared and then added to slurries of aluminum oxide dihydrate. Amounts of the starting materials are shown in Table 9. Stirring at ambient temperature and heating are carried out as described in Table 10 and 30 has the range of reaction composition as shown in Table 11. Aliquots of the reaction mixture are put into autoclaves lined with TEFLON* of about 15 ml internal capacity and sealed. The autoclaves are heated at the temperature and for the time indicated. The resulting

~5 products are white solids which are recovered by slurrying the contents of the reactor with deionized water and allowing the solids to settle. This dried at room temperature in air overnight.

TABLE 9

— Denotes no data Calculating from the information above it can be seen that there is a range of molar ratios of the reaction composition as follows in Table 11 and that said compositions are further characterized by Table 1

10

1.5

A solution prepared with 8.9 g of orthophos¬ 0 phoric acid (85 percent H3PO2J) and 6.0 g of water is added to a slurry of 5.3 g of aluminum oxide dihydrate in 6.0 g of water. This precursor mixture is homogenized for several minutes. A second solution is prepared by adding 18.3 g of aqueous 55 weight percent 5 tetrabutylammonium hydroxide (TBA) and 0.928 g of fumed silica to 10.9 g of water. This second solution is added with mixing and the resulting reaction mixture is homogenized for 90 minutes. The reaction mixture has 0 the following composition:

1.0 TBA: Al₂θ3: P 0₅: 0.4 Si0 : 52 H₂0

Portions of the mixture are transferred into TEFLON* lined stainless steel autoclaves of 15 ml internal 5 capacity to give approximately 60 percent filling by volume. The autoclaves are heated to 150°C at autogenous pressure for more than 44 hours. The product is recovered as described in Example 8 and is characterized by Table 1.

Example 10

A solution is prepared with 8.9 g of 85 percent orthophosphoric a:cid and 6 g of water. This is added to a slurry of 5.3 g of aluminum oxide dihydrate in 6 g

10 of water. This is homogenized for several minutes and 2.5 g of a 40 percent low sodium colloidal silica is added. The resulting gel is aged at room temperature without stirring for one hour. A solution of 10.9 g water and 18.3 g of 55 percent tetrabutylammonium T5 hydroxide is then added. The reaction composition is as follows:

TBA: A1₂0₃: P₂0₅: 0.4 Si0₂: 50 H₂0

20 The gel is heated at 150°C for 41 hrs as described in previous examples. The white solid is recovered by slurrying the contents of the reactor with deionized water and allowing the solids to settle. The solid is dried at room temperature in air overnight and is 25 characterized by Table 1.

Exam le 11

A solution prepared with 11.5 g of -_3Q orthophosphoric acid (85 percent ^PO^) and 9.8 g of water is stirred for 20 minutes. A slurry consisting of 6.8 g of aluminum oxide dihydrate and 20 g of water and stirred for 15 minutes. The phosphoric acid solution is then added to the aluminum-containing 35' mixture with stirring. About 0.93 g of fumed silica is then added. The silicoaluminumphospha^*te precursor mixture is homogenized for 2 hours, and during this time the pH of the mixture increases from 0.9 to 1.6, stabilizing at 1.6.

Next, about 6.87 ml of dipropylamine (DPrA) is added to the mixture with constant agitation. The gel is then further homogenized for 4 more hours. This gel has the oxide composition

10 DPrA: A1₂0₃: P2O5: 0.3 Si0₂: 40 H₂0

Portions of the mixture are transferred to TEFLON* lined autoclaves and heated to 142°C at autogenous pressure for at least 24 hours. The white solid

_.._[. product is recovered by slurrying the contents of each autoclave in water, stirring for several minutes, allowing the solid to settle and discarding the supernatant liquid. The solid is then filtered and dried in an oven at 100°C and is characterized by Table 0 1.

Example 12

About 11.5 g of orthophosphoric acid (85 _c percent H3PO₁1) is dissolved in 9.7 g of water and stirred. This solution is added dropwise to a slurry of 6.7 g of aluminum oxide dihydrate and 20 g of water. The resulting precursor mixture is aged while stirring at room temperature for a period of time as shown in 0 Table 13- At this point an amount of a metal compound as shown in the same table is added with stirring at room temperature. Total stirring time, defined as stirring of the Al₂θ3/P₂θ5 mixture both before and after adding the total compound, is given in the table. 5 Separate reaction mixtures are prepared using magnesium, cobalt, and zinc in according varying proportions. Water proportions are also shown. In all cases water is used. An amount of dipropylamine (DPrA), also as shown in the table, is then added dropwise. The reaction mixture is heated at in a- stainless steel TEFLON* lined autoclave for the time shown in the table. The resulting solid is recovered by slurrying the contents of the reactor with deionized water and allowing the solids to settle. The solid is dried at room temperature in air overnight and is characterized by Table 1. Specific reactants and process variables are shown in the Table 12.

TABLE 12 Run 1 Run 2 Run Run 4 Run 5 Run 6

Example 13

In order to better understand the nature of the VPI-5 compositions of the invention, showing the unique X-ray diffraction pattern of Table 1 as described above, adsorption experiments were carried out on samples of VPI-5 previously heated to at least about 350°C for at least about one hour, and then cooled to room temperature under vacuum. The samples were then 0 exposed to atmospheres of given adsorbates until an equilibrium uptake was obtained. Equilibrium was defined as constant weight of the sample plus adsorbate for at least about 2 hours. The results of these experiments are summarized in Table 13, which includes 5 adsorption data for water, oxygen, nitrogen, cyclohexane, neopentane, and triisopropylbenzene.

That table shows adsorption data for VPI-5 prepared using two different structure directing 0 materials, dipropylamine and tetrabutylammonium hydroxide. It also shows adsorption data for three other reported materials, which are zeolite Y (described in U.S. Patent 3,216,789) and molecular _c- sieves AlPO^-5 and AlPOi_j-8 (as described in U.S. Patent 3,414,602). From the table it can be inferred that molecules having a kinetic diameter In the range of from about 3 Angstroms to about 14 Angstroms can be admitted into the VPI-5 intracrystalline free 0 micropores.

5 TABLE 1 3

1 Activated by heating to 350° C. in vacuum overnight. *Tetrabutylammonium hydroxide

2 U. S. Patent 4, 310,440 **Dipropylamine

3 Breck, D. W., Zeolite Molecular Sieves (John Wiley, publisher 1974) --Denotes no data

4 All performed at P/Po = 0.4

Claims

2>βCLAIMS:

1. Crystalline aluminumphosphate compositions having three-dimensional microporous crystal framework structures whose chemical composition expressed in terms of mole ratios of oxides is

A1₂0₃: 1.0+0.2 P₂0₅;

and which is further defined as having an X-ray powder diffraction pattern characterized by d spacings at less than about 40 degrees two-theta as measured using 0 copper K-alpha radiation that are as shown in Table 1.

2. The compositions of Claim 1 having intracrystalline free micropores such that molecules having a kinetic diameter in the range of from about 3 _£- Angstroms to about 14 Angstroms can be admitted therein.

3. The compositions of Claim 2 wherein the molecules are triisopropylbenzene. 0

4. The compositions of Claim 1 showing an argon adsorption isotherm in comparison with the argon adsorption isotherm of zeolite X(Na) as shown in Figure 1. 5

5. The compositions of Claim 1 wherein the Al₂θ and P₂0IJJ form an oxide lattice.

6. The compositions of Claim 1 further comprising a structure-directing agent such that the chemical composition expressed in terms of mole ratios of oxides is

xR: A1₂U3: 1.0+0.2 P 0₅;

10 wherein

Al₂θ and P₂θ5 form an oxide lattice;

R represents a structure-directing agent; and

15 x>0.

7. The compositions of Claim 6 wherein the structure-directing agent is dipropylamine, „ diisopropylamine, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, dipentylamine, tripentylamine, or tributylamine.

8. The compositions of Claim 6 wherein the

_?c- structure-directing agent is in an amount of 0.02 mole to 4 moles for each mole of Al₂θ «

9. The compositions of Claim 6 wherein the structure-directing agent is in an amount of 1 mole for

10. The compositions of Claim 16 wherein the structure-directing agent can be desorbed.

11. The composition of Claim 1 or 6 further 5 comprising 0.001 to 0.5 mole of at least one metal oxide of silicon, magnesium, titanium, cobalt, tin, or zirconium.

12. The composition of Claim 11 wherein the l₂θ » P θ5 and metal oxide form an oxide lattice.

13- The compositions of Claim 1 or 6 wherein the X-ray powder diffraction pattern of the compositions after heating to at least 600°C is

10 characterized by d spacings at less than about 40 degrees two-theta as measured using copper K-alpha radiation that are substantially as shown in Table 1.

14. The compositions of Claim 24 wherein the

15 silicon oxide is fumed silica, aqueous colloidal silica, tetraethylorthosilicate, or mixtures thereof.

15. A method of preparing crystalline aluminumphosphate compositions having three-dimensional ₀ microporous crystal framework structures such that the chemical composition of the precursor mixture expressed in terms of mole ratios of oxides is

A1₂0₃J 1.0+0.2 P₂0₅? 10-100 H₂0, 5 further comprising 0.02 to 4.0 moles of a structure- directing agent for each mole of Al θ3, the method comprising :

(1) admixing an aluminum source, a phosphorus

30 source, and water to form a precursor mixture?

(2) admixing the precursor mixture and the structure-directing agent to form a reaction mixture; and

,r (3) heating the reaction mixture under reaction conditions such that a crystalline solid having an X- ray diffraction pattern characterized by d spacings that are as shown in Table 1.

16. The method of Claim 15 wherein the mole ratio of P₂0₅ to Al₂θ3 is 0.9 to 1.1.

17. The method of Claim 15 wherein the mole ratio of water to Al₂θ3 is 20 to 70.

18. The method of Claim 15 wherein the aluminum source is elemental aluminum, hydrates of aluminum, aluminum oxides, aluminum alkoxides, or mixtures thereof.

19. The method of Claim 15 wherein the phosphorus source is orthophosphoric acid, elemental phosphorus, phosphorus oxide, esters of phosphoric acid, or mixtures thereof.

20. The method of Claim 15 wherein the structure-directing agent is dipropylamine, diisopropylamine, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, dipentylamine, tripentylamine, or tributylamine.

21. The method of Claim 15 wherein the compositions have intracrystalline free micropores such that molecules having a kinetic diameter in the range of 3 Angstroms to 14 Angstroms can be admitted therein.

22. The method of Claim 15 wherein the molecules are triisopropylbenzene.

23. The method of Claim 15 showing an argon adsorption isotherm in comparison with the argon adsorption isotherm of zeolite X(Na) as shown in Figure 1.

24. The method of Claim 15 wherein the heating is done at a temperature of 50°C to 200°C.

25. The method of Claim 15 wherein the heating is done for a 1 hour to about 10 days.

26. The method of Claim 15 wherein the aluminum 0 source and a portion of the water are mixed separately and the phosphorus and a second portion of the water are mixed separately, and then the two mixtures are combined to form the precursor mixture. -5

27. The method of Claim 15 wherein the precursor mixture is aged from 1 hour to 5 hours such that a substantially constant pH is reached.

28. The method of Claim 15 wherein a metal H source of silicon, magnesium, cobalt, titanium, tin, zinc, zirconium or mixtures thereof is added to the precursor mixture such that the chemical composition of the resulting precursor mixture expressed in terms of _c- mole ratios further comprises a total of 0.001 mole to 3 moles of the oxide of the metal.

29. The method of Claim 28 wherein the metal source is a silicon source and the precursor mixture 0 comprises from 0.1 to 1 mole of silicon dioxide.

30. The method of Claim 29 wherein the silicon source is fumed silica, aqueous colloidal silica, tetraethylorthosilicate, or mixtures thereof. 5 31. The method of Claim 15 wherein the crystalline solid is further subjected to washing with an acid solution, a salt solution, an organic solvent or deionized water; drying; and thermal treatment.