AU612713B2 - Crystalline aluminophosphate compositions - Google Patents

Description

K IPATEN I PLIA (51) r__ (43) AiJ-A-22753/88

I

PCT WORLD INTELLECTUAL PROPERTY ORGANIZATION INTERNATIONAL APPLICATION PUBT PATERATIN TREATY (PCT) INTERNATIONAL APPLICATION PUBLI D N F T1E PAT NT PERATION TREATY (PCT) (51) International Patent Classification 4 (11) International Publication Number: WO 89/ 01912 C01B 25/36 Al (43) International Publication Date: 9 March 1989 (09.03.89) (21) International Application Number: PCT/US88/02910 (22) International Filing Date: 24 August 1988 (24.08.88) (31) Priority Application Numbers: 090,801 207,850 (32) Priority Dates: 28 August 1987 (28.08.87) June 1988 (15.06.88) (33) Priority Country: US (71) Applicant: THE DOW CHEMICAL COMPANY [US/ US]; 2030 Dow Center, Abbott Road, Midland, MI 48640 (US).

(72) Inventors: DAVIS, Mark, E. 710 Cedarview Drive, Blacksburg, VA 24060 GARCES, Juan, M. 5217 Cortland Street, Midland, MI 48640 SAL- DARRIGA, Carlos, H. Carrera 47 #63A36, Medellin MONTES DE CORREA, Maria del Consuelo 38-A Terrace View, Blacksburg, VA 24060

(US).

(74) Agent: BIEBER, James, The Dow Chemical Company, P.O. Box 1967, Midland, MI 48641-1967 (US).

(81) Designated States: AT (European patent), AU, BE (European patent), CH (European patent), DE (European patent), FI, FR (European patent), GB (European patent), HU, IT (European patent), JP, KR, LU (European patent), NL (European patent), NO, RO, SE (European patent), SU.

Published With international search report, A.O. LP. 1 MAY 1989 AUSTRALIAN4 3 1 MAR 1989 PATENT

OFFICE

I_

(54) Title: CRYSTALLINE ALUMINUMPHOSPHATE COMPOSITIONS (57) Abstract Crystalline aluminumphosphate compositions having threedimensional microporous crystal framework structures whose chemical composition expressed in terms of mole ratios is A1 2 0 3 :i.0±0.2 P 2 0 5 are disclosed. Adsorption data shows that the com- Z a/A/ X(Na) positions 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 I. 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 A1 2 0 3 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 0 /o0" an aluminumphosphate composition of the given X-ray diffraction pattern is formed. P/Po Metal substituted aluminumphosphate conpositions 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 siliron, magnesium, zinc, tin, zirconium, titanium, cobalt, and mixtures thereof.

WO 89/01912 PCT/US88/02910 1 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.

Mo'lecular 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 aluminosilicate composition.

The naturally occurring and synthetic analogues of the zeolites include over a hundred compositions.

1 Zeolites are, by definition, tectosilicates, which means that their framework comprises tridimensional structures made of Si04 4 and A10 4 -5 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 WO 89/01912 PCT/US88/02910 -2linkage of Ti0 tetrahedra, wherein T represents either silicon or aluminum atoms.

Zeolites are synthesized in general by 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 zeolitic products can be obtained from the same starting composition, depending on the raw materials, mixing methods, and crystallization procedures employed.

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 aluminvmphosphates with 2 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, 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 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 beryllium, boron, gallium, iron, titanium, and phosphorus are used as substitutes for the silicon or' Sr WO 89/01912 PCT/US88/02910 -3aluminum. These are described in E. Moretti et al., "Zeolite Synthesis in the Presence of Organic Components," Chimica. e Industria, 67 (1985) 21-34.

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 TO 4 tetrahedra. To date, while there have been 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 AlPO 4 -8 (see example 62-A of that patent) which is reported to significantly adsorb perfluorotributylamine, PFTBA [(C 4

F

9 3 PFTBA is known to have a kinetic diameter of about 10 A. See R.M. Barrer, Zeolites and Clay Minerals (1978) 7. A 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 definitively whether the PFTBA molecules are adsorbed in the micropores themselves, in capillary pores 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 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," Izvestiya Akademii Nauk SSSR 17, 6 (June 1981) 1018-1021.) WO 89/01912 PCT/US88/02910 -4- Accordingly, there are now pr-_v.ded crystalline aluminumphosphate compositions having three-dimensional microporous crystal framework structures whose chemical composition expressed 'n terms of mole ratios of oxides is A1 2 0 3 1.0+0.2 P 2 0 5 and which are 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 as shown in Table 1.

The present invention further provides crystalline aluminumphosphate compositions having three-dimensional microporous crystal framework structures comprising a structure-directing agent, such that the chemical composition expressed in terms of mole ratios is: xR: A1 2 0 3 1.0+0.2 P 2 0 5 wherein Al20 3 and P205 form an oxide lattice; R 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 as shown in Table 1.

The present invention also provides a method of preparing these crystalline aluminumphosphate compositions from a precursor mixture whose chemical composition expressed in terms of mole ratio- is r r WO 89/01912 PCT/US88/02910 A1 2 0 3 1.0+0.2 P 2 0 5 10-100 H 2 0, further comprising 0.02 to 4.0 moles of a structuredirecting agent for each mole of A1 2 0 3 comprising .the steps of admixing an aluminum source, a phosphorus source, and water to form the precursor mixture, admixing the precursor mixture with the structuredirecting agent to form a reaction mixture, and reacting the reaction mixture under conditions such that a crystalline aluminumphosphate composition, oharacterized by d spacings at less than about degrees two-theta as measured using copper K-alpha radiation that are substantially as shown in Table 1, is formed.

The present invention further provides crystalline metal substituted aluminumphosphate compositions having three-dimensional microporous crystal framework structures comprising a structuredirecting agent, such that the chemical composition expressed in terms of mole ratios is xR: A1 2 0 3 1.0+0.2 P 2 0 5 0.001-0.5 MOz/2: 10-100 H 2 0; wherein A1 2 0 3

P

2 0 5 and MOz/2 form an oxide lattice; R is a structure-directing agent; x>0; M is a metal; z is the oxidation state of M; and MOz/ 2 is at least one metal oxide; the chemical composition further comprising one or more charge-compensating species; 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 Sas shown in Table 1.

c i i WO 89/01912 PCT/US88/02910 -6- 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 Ag120: l uGU.5 P 2 0 5 0.001-0.5 MOz/ 2 10-100 H 2 0, wherein M is a metal; z is the oxidation state of M; and MOz/2 is at least one metal oxide; the chemical composition further comprising from one or more chargecompensating species'and 0.02 to 4 moles of a structure-directing agent for each mole of A1 2 0 3 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 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 e invention, denoted VPI-5, and for Zeolite X(Na).

WO 89/01912 PCT/US88/02910 -7- The compositions of one embodiment of the present invention are synthetic, crystalline aluminumphosphate materials, hereafter denoted as "VPIwhich 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 aluminumphosphat? 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 A1 2 0 3 1.0±0.2 P 2 0 5 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 between about three degrees two-theta and about 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 for medium. Peaks of lesser intensity, described as having weak intensities, are thus excluded from this definition. The d spacings rem±in substantially the same after VPI-5 samples are heated WO 89/01912 PCT/US88/02910 -8to at least about 600°C. This heating can take place, for example, under vacuu.m, 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.

I- 1 WO 89/01912 WO 8901912PCT/US88/0291 0 -9- TABLE 1 X-Ray Powder Diffraction Data for As-Synthesized Two-theta _(degrees) 5.36 9.32 10.75 14.35 16.16 18.68 Z1i .6(5 2 1.92 22.-39 22.56 23.59 24.46 26.12 27,,.17 28.19 28.96 29.48 30.28 30.88 32-71 34.05 35.86 38.32 d (A) 16.48 9.49 6 23 6.17 5.48 4.75 4.10o 4.05 3.97 3.94 3.77 3.64 3.41 3.28 3. 17 3.08 3.03 2.95 2.90 2.74 2.63 2.50 2.35 1/10 M% vs w In In w In In In In in in w w rn w w w w w In w w

W

WO89/01912 PCT/US88/02910 Another characterization of the aluminumphosphates 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 xR: A1 2 0 3 1.0±0.2 P 2 0 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 A1 2 0 3 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 OMNISORP* 360 instrument (*OMNISORP 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 Horvath et al., "Method for the Calculation of Effective Pore Size Distribution in Molecular Sieve Carbon", J. Chem. Eng. of Japan 16, 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 i r WO 89/01912 PCT/US88/02910 -11has pores substantially larger than Zeolite X(Na).

Thus, from the experiments described above, it S 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 A1 2 0 3 to P 2 0 5 In general these compositions are defined by the following molar ratios: A1 2 0 3 1.0±0.2 P 2 0 5 0.001-0.5 MOz/ 2 10-100 H 2 0 In this formula M is a metal, a is the oxidation state of M, and MOz/ 2 is at least one metal oxide. For example, the formula showing the molar ratios of the silicoaluminumphosphate compositions is: A-.03: 1.0±0.2 P 2 0 5 0.001-0.5 Si0 2 10-100 The structure-directing agent is present in-the same proportion for the metal substituted aluminumphosphates as for the unsub. ituted aluminumphosphate compositions, and the same choices as to aluminum and phosphorus sources as well as structure directing agents will be applicable. Similarly, the structuredirecting agent may or may not remain in the final silicoaluminumphosphate VPI-5 compositions., depending c .i i- i ,r i WO 89/01912 PCT/USbS/02910 -12on whether desorption or decomposition has occurred.

The chemical composition further comprises one or more species that are charge-compensating for the metalsubstituted aluminumphosphates species such that the 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.

Other elements from sources capable cf forming oxides can also be substituted into the basic aluminumphosphate crystal framework structures without significant effect on the X-ray powder diffraction pattern or general oxide lattice structure. These include, for exam.pe, substitute metals such as titanium, tin, cobalt, zinc, magnesium, zirconium, and mixtures thereof.

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 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 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.

The combining of the components can be done in a variety of ways, such that the described I f WO 89/01912 PCT/US8/02910 -13compositions are produced. For example, the aluminum source can be admixec 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 aluminumphosphate compositions of the present invention can be selected from a number of possible choices. Possible I -na~uu~ WO S9/01912 PCT/US88/02910 -14sources of phosphorus include, for example, elemental phosphorus, orthophosphoric acid (H 3 PO4), phosphorus oxide, esters of phosphoric acid, and mixtures of tbhse. Of these, orthophosphoric acid is preferred.

Preferred aluminum sources includ- hi-ydrates 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 sou:rces. The phosphorus source 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 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 invention, the acetate dihydrates or tetrahydrates of the metals, cobalt acetate tetrahydrate, zinc acetate L.hydrate, or magnesium acetate tetrahydrate, are preferred, but other metal-containing compounds are also possible sources. The metal can also be supplied 235 as a complex ion, such as 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 3 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 reaction mixture. It is preferable to age this WO 89/01912 PCT/US88/02910 reaction mixture for 1 to 2 hours, again to allow for pH stabilization.

Various effective structure-directing agents are dipropylamine, diisopropylamine, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, dipentylamine, tripentylamine, tributylamine, alkylammonium and alkylphosphonium compounds in general, and mixtures of these. Of these, dipropylamine, tetrabutylammonium hydroxide and dipentylamine are preferred, and more preferred is tetrabutylammonium hydroxide. Related molecules may also serve as structure directing agents it the present invention.

The proportions of the reactants can be varied within given ranges. ,Basing proportions on an A1203 molar value of 1, the structure directing agent to A1 2 0 3 molar ratio can be preferably 0.02 to 4, more preferably 0.2 to 2, and most preferably 1; the P205 to A1203 molar ratio can be preferably 0.8 to 1.2, more prse&rably 0.9 to 1.1, and most preferably 1; and the water to A1 2 0 3 molar ratio can be preferably 10 to 100, more preferably 30 to 70, and most preferably 35 to When silicon or another metal is added to produce the metal substituted aluminumphosphate of the present invention, the above ratios are still applied, and in addition the MOz/2 to A1203 molar ratio can be preferably from 0.001 to 0.5 mole of metal oxide per mole of A1203. 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 A1 2 0 3 be 0.2 to 0.5 for silicon dioxide, and most preferred that it be 0.3 to 0.4, while it is more preferred that the ratio to A1 2 0 3 i -L~ W 0 39/01912 PCT/US88/02910 -16of 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, the alumiinum 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 preferably aged until a substantially constant pH is attained, the reaction mixture is 2 reacted under conditions such that a crystalline solid having the X-ray powder diffraction pattern by which compositions are defined is formed. For this, known methods of heating are preferably employed.

Autoolaving in bombs lined with TEFLON* (*TEFLON is a risred and convenient means of achieving this. Other types of reactors can alternatively be used. The temperat preferably ranges 500C to 200°C, and 1000°C0 500C is more preferable. The reaction can ferably be carried out under pressure, F example, autogenous pressure, or at atmo eric pressure.

e of reaction varies, in part depending on t e-'mperature used. Insufficient heating may lead to Samorphous products, and excessive heating may result in (4 1 I I 16a trademark of Du Pont de Nemours, Inc. used herein the claims and description) is one effective and convenient means of achieving this. Other types of reactors can alternatively be used. The temperature preferably ranges 50 0 C to 200 0 C, and 100 0 C to 150 0 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 'o amorphous products, and excessive heating may result in *sot* o/ o r i D I i WO 89/01912 PCT/US88/02910 -17the formation of amorphous products or undesirable phases A time of 2 hours to 50 hours in conjunction with a temperature of 100 0 C to 150 0 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.

i WO 89/01912 PCT/US88/02910 -18- 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 orthophosphoric acid (85 percent H 3

PO

4 and 100 g water.

The resulting precursor mixture is aged without agitation for 2 hours at room temperature. 186 g of 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: TBA: A1 2 0 3

P

2 0 5 50 H 2 0 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

H

3

PO

4 and 11.0 g water and aged at room temperature 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.

I

WO 89/01912 PCT/US88/02910 -19- TABLE 2 Al 2 0 .2H 2 0 2 Composition 6.25 6.59 6.73 6.94 7.15 7.29 7.63

TBA:

TBA:

TBA:

TBA:

TBA:

TBA:

TBA:

P,.05: P 2 0 1 P205 P205: P205: P205: P205: 0.90 0.95 0.97 1.00 1.03 1.05 1.10 A1 2 0 3 A1 2 0 3 A1 2 0 3 A1 2 0 3 A1 2 0 3 A1 2 0 3 A1 2 0 3 40 40 40 40 40 40 H 2 0 40 H 2 0 The reaction mixtures are heated at 150 0 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 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 br for about 20 minutes.

stirred with a magnetic bar for about 20 minutes.

WO 89/01912 PCT/US88/02910 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: TBA: A1 2 0 3

P

2 0 5 52 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 i Example 1 and is characterized as in Table 1.

Example 4 About 11.50 g of orthophosphoric acid percent concentration H 3 P0 4 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 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 Sin Table 3: To the foregoing precursor mixture about 5.075 g of di.ropylamine (DPrA) is added while

I

WO 89/01912 PCT/US88/02910 -21- TABLE 3 Time (min.) 0.72 1.00 1.20 1.50 1.60 1.70 1.70 0 110 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: DPrA: Al 2 03: P 2 0 5 40 H 2 0 This reaction mixture is then transferred to five TEFLON* lined stainless steel autoclaves labeled, respectively, 1, 2, 3, 4, anO 5, and heated under 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 -i ,e .F I i.:il WO 89/01912 PCT/US88/02910 -22- TABLE 4 Run Time 1 20 hr.

2 24 hr. 5 min.

3 25 hr. 10 min.

4 25 hr. 10 min.

5 25 hr. 10 min.

A white solid is recovered by separately 15 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 Five solutions of orthophosphoric acid 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.

61 I I' i r

I

WO 89/01912 PCT/US88/02910 -23- TABLE Component A1203

H

3

PO

4 DPrA Water Run 1 13.75 23.0 10.15 59.6 Run 2 6.875 11.5 5.075 29.8 Run 3 6.875 11.5 5.075 29.8 Run 4 (g) 13.75 23.0 10.15 59.6 Run 6.875 11.5 5.07 29.8 Each reaction mixture is then heated at the temperatures and times shown in Table 6 in a stainless TEFLON*-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.

WO 89/01912 PCT/US88/02910 -214- TABLE 6~ *Synthesis Cond iion Stirring of precursor mixture (m i Temperature during stirring Svrring of reaction mixture (m i pH a.fter stirring Heating time (hn-u rs) Heating temperature Pun 11Q Run 2 Run R 3 u n Run 4 60 20 ambient ambient 55'C 60'C ambient 80 3.99 24.

135 1 d;J j 150 125 142 Denotes no data The reaction compos.ition of' all runs is DPrA: A1 2 0 3 37 H20, and is further characterized by Table 1.

Example 6 Four solutions of orthophosphoric acid percent H 3 POi4) 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 i~n that table. The resulting prpnursor mixtures are stirred and pH is measured. Dipen1tylamirne (DPtA) is added dropwise and each of the resulting precursor mixture(s) is again 6tir'ed for the time shown.

uiU~ I II 1 WO 89/01912 PCT/US88/02910 TABLE 7 Component A1 2 0 3

H

3

PO

4 DPtA Water Run 1 5.3 8.9 7.89 12 Run 2 10.6 17.8 15.78 36 Run 3 15.75 23.0 15.78 .59.6 Run 4 6.875 11.5 7.89 39.8 The reaction mixtures are heated in stainless steel TEFLON*-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.

n i_ WO 89/01912 PCT/US88/02910 -26- TABLE 8 Synthesis Condition Stirring of precursor mixture (minutes) Temperature during stirring Stirring of reaction mixture (min.) pH Heating time (h rs.) Heating temperature

°C

Run 1 Run 2 Run 3 Run 4 20 ambient ambi"it 55 0 C ambient 1.78* 20 1.90** 44 142 1.70* 142 Denotes precursor mixture Denotes reaction mixture Example 7 About 8.9 g of orthophosphoric acid H 3

PO

4 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 perce-t dipentylamine is then added to the homogenc vecuror mixture WO 89/01912 PCT/US88/02910 -27while 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 following molar ratio composition: DPtA: Al 2 0 3

P

2 0 5 40 H 2 0 Aliquots (each about 25 percent of the total) of the aged mTixture are transferred to autoclaves lined with TEFLON* and heated at 150 0 C under autcgenous 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 dried in air at 100 0 C for about 30 minutes.

Example 8 Using the same procedure as in previous 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 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 products are white solids which are recovered by slurrying the contents of the reactor with deionized silicon dioxide, and most preferred that it be 0.3 to 0.4, while it is more pr'eferred that the ratio to A1 2 0 3 WO 89/01912 PCT/US88/029 -28water and allowing the solids to settle. This dried at room temperature in air overnight.

TABLE 9 Cornpo ne nt Runi1 Run 2 Run 3 Run 4 Run (92I 192 192 III (q) A203 H 3 P0 4

TBA

Water 5.3 8.9 18.3 32.9 11.15 17-8 36.6 11.6 11.15 17.8 36.6 25.65 11.15 17.8 36.6 39.69 5.72 8.9 18.3 TABLE Synthesis Condition Run Run Run 1 2 3 Run Run 4 -5 Run 6 Agiijgof precursor mixture (mmi Stirring of reaction mixture (mm.

Heating time Heating temperature 0C aged 45 45 45 45 5 h rs.

145 5 days 150 5 days 150 5 days 150 41 h rs.

150 44 Inrs.

150 Denotes no data 0 i- i WO 89/01912 PCT/US88/02910 -29- 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.

TABLE 11 Run Composition 1 TBA: Al 2 03: P 2 0 5 48 2 TBA: A1 2 0 3 P205: 20 H 2 0 3 TBA: A1 2 0 3

P

2 0 5 30 H 2 0 4 TBA: A1 2 0 3

P

2 0 5 40 H 2 0 5 TBA: A1 2 0 3

P

2 0 5 50 Example 9 A solution prepared with 8.9 g of orthophosphoric acid (85 percent H 3 PO4) 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 preoursor mixture is homogenized for several minutes. A second solution is 2 prepared by adding 18.3 g of aqueous 55 weight percent tetrabutylammoniim 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 the following composition: TBA: A1 2 0 3

P

2 0 5 0.4 Si02: 52 Portions of the mixture are transferred into TEFLON* Slined stainless steel autoclaves of 15 ml internal capacity to give approximately 60 percent filling by volume. The autoclaves are heated to 150'C at WO 89/01912 PCT/US88/02910 autogenous pressure for more than 44 hours. The product is recovered as described in Example 8 and is characterized by Table 1.

S Example A solution is prepared with 8.9 g of 85 percent orthophosphoric acid and 6 g of water. This is added to a slurry of 5.3 g of aluminum oxide dihydrate in 6 g of water. This is homogenized for several minutes and 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 hydroxide is then added. The reaction composition is as follows: TBA: A1 2 0 3

P

2 0 5 0.4 Si02: 50 H 2 0 SThe 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 characterized by Table 1.

Example 11 A solution prepared with 11.5 g of orthophosphoric acid (85 percent H 3 P0 4 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 mixture with stirring. About 0.93 g of fumed silica is then added. The silicoaluminumphosphate precursor I l WO 89/01912 PCT/US88/02910 -31mixture 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 DPrA: A1 2 0 3

P

2 0 5 0.3 Si0 2 40 Portions of the mixture are transferred to TEFLON* lined autoclaves and heated to 142 0 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 1000C and is characterized by Table 1.

Example 12 About 11.5 g of orthophosphoric acid percent H 3 P0 4 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 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 A1 2 0 3

/P

2 0 5 mixture both before and after adding the total compound, is given in the table.

3 Separate reaction mixtures are prepared using magnesiums cobalt, and zinc in according varying i MIMMIr- WO 89/01912 PCT/US88/02910 -32proportions. 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 Runi1 Run 2 Run 3 Run 4 Run 5 Run 6 Metal Magnesium Compound acetate Cobalt acetate Zinc Cobalt Magnesium 2ijnc acetate acetate acetate acotate Amount (g) Stirring of precursor mixture (min.) DPrA Amount (ml) Heating time Temp- -21 60 5-03,.

5 hrs.

150 0

C

25 .25 0.25 60 90 135 0.21 105 6.88 0-22 135 6.88 t-,J CtCD (D 'S Ct Ct D In (D (D o al 0 1 p En r- 0 acr S CD

(D

5.03 5.03 6.88 3 hrs. 3 hrs. 24+ 24 +hrs. 24+ H rs. h rs- 150 0 C 1 50 0 C 142 0 C 142 0 C 142 0

C

L

WO 89/01912 PCT/US88/02910 -34- Example 13 In order to better understand the nature of the compositions of the invention, showing the unique SX-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 0 C for at least about one hour, and then cooled to room temperature under vacuum. The samples were then exposed to atmospheres of given adsorbates until an equilibrium uptake was obtained. Equilibrium was defined as constant weight of the samiple plus adsorbate for at least about 2 hours. The results of these experiments are summarized in Table 13, which includes adsorption data for water, oxygen, nitrogen, cyclohexane, neopentane, and trtisopropylbenzene.

That table shows adsorption data for prepared using two different structure directing 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 sieves A1P0 4 -5 and AlPO 4 -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 micropores.

I

TABLE 13 cm3Jg Adsorbed Molecule Kinetic diamneter

A

Pressure Torr- Temp.

c VPi-51 made with TBA* VPI-51 made with DPrA** Al P0 4 -8qz Al P-0 4 -5 A Nay 3

H

2 0 2.651 18-20 23-26 0-368 0.384 t0.319 0.22 0.363 02 3-46 100 liq.. N 2 0.248 0.233 0.329 100 liq. 02 I -0.7 0.146 755 Iiq- 02 0 t 5

N

2 3.64 100 liq- N 2 0-219 0.334 740 0-249 hexane 4-20 40 23-26 0.191 0.139 0.288 cyclo- 6.00 65 26 0.183 0.145 0.226 hexane neopen- 6.20 755 26 0-163 -0.137 0.245 tane 501 0.073 1 1 triisopropylbenzene 8.4-9.5 vapor pressure 20-23 0-150 Activated by heating to 3500 C in vacuum overnight.

U. S. Patent 4,310,440 Breck, D. Zeolite Molecular Sieves (John Wiley, publisher 1974) AltI per-formed at PIPo 0-4 *Tetrabutylammonium hydroxide **Dipropylamine -Denotes no data

Claims (25)

1. Crystalline aluminumphosphate compositions having three-dimensionp.l microporous crystal framework structures whose chemical composition expressed in terms of mole ratios of oxides is Al 2 0 3 1.0+0.2 P 2 0 5 and which is further defined as having an X-ray powder diffraction pattern characterized by d spacings at lens than-abe-u-- 40 degrees two-theta as measured using 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 abou- 3 Angstroms to -a-bou 14 Angstroms can be admitted therein.

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

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. L WO 89/01912 PCT/US88/02910 -37- The compositions of Claim 1 wherein the Al 2 0 3 and P 2 0 5 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 s xR: A1 2 0 3 1.0+0.2 P 2 0 5 wherein Al 2 0 3 and P 2 0 5 form an oxide lattice; R represents a structure-directing agent; and x>0.

7. The compositions of Claim 6 wherein the structure-directing agent is dipropylamine, diisopropylamine, tetrabutylant.:-nium hydroxide, tetra,;,opylammonium hydroxide, dipentylamine, tripentylamine, or tributylamine.

8. The compositions of Claim 6 wherein the structure-directing agent is in an amount of 0.02 mole to 4 moles for each mole of A1 2 0 3

9. The compositions of Claim 6 wherein the structure-directing agent is in an amount of 1 mole for each mole of Al20 3 The compositions of Claim 6 wherein the structure-directinr agent can be desorbed.

11. The composition of Claim 1 'r 6 further 39 comprising 0.001 to 0.5 mole of at least one metal WO 89/01912 PCT/US88/02910 -38- oxide of silicon, magnesium, titanium, cobalt, tin, or zirconium.

12. The composition of Claim 11 wherein the A1 2 0 3 P 2 0 5 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 0 C is characterized by d spacings at less than abut degrees two-theta as am~iured using copper K-alpha radiation that are substantially as shown in Table 1.

14. The compositions of Claim 24 wherein the silicon oxide is fumed silica, aqueous colloidal silica, tetraethylorthosilicate, or mixtures thereof. A method of preparing crystalline aluminumphosphate compositions having three-dimensional microporous crystal framework structures such that the chemical composition of the precursor mixture expressed in terms of mole ratios of oxides is A1 2 0 3 P 2 0 5 10-100 H 2 0, further comprising 0.02 to 4.0 moles of a structure- directing agent for each mole of A1 2 0 3 the method comprising admixing an aluminum source, a phosphcrus source, and water to form a precursor mixture; admixing the precursor mixture and the structure-directing agent to form a reaction mixture; and (3j heating the ieartion mixture under reaction conditions such that r crystalline solid having an X-. fAVS tI. WO 89/01912 PCT/US88/02910 -39- ray diffraction pattern characterized by d spaci \gs that are as shown in Table 1.

16. The method of Claim 15 wherein the mole ratio of P 2 0 5 to A1 2 0 3 is 0.9 to 1.1.

17. The method of Claim 15 wherein the mole ratio of water to Al 2 0 3 is 30 to

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 phosphoi ic acid, or mixtures thereof. The method of Claim 15 wherein the structure-directing agent is dipropylamine, diisopropylamine, tetrabutylamm.onium hydroxide, tetrapropylammonium hydroxide. dipentylamine, tripentylamine, or tributylamine.

21. The method of Clain 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 ,vl37 WO 89/01912 PCT/US88/02910 adsorption isotherm of zeolite X(Na) as shown in Figure

24. The method of Claim 15 wherein the heating S is done at a temperature of 500C to 2000C. The method of Claim 15 wherein the heating 2-5o0 ours a- Op- so is done for a 1 hoar to about 10 days.

26. The method of Claim 15 wherein the aluminum 1 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.

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 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 mole ratios further comprises a total of 0.001 mole to O'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 comprises from 0.2 05mole of silicon dioxide. The retAhod of Claim 29 wherein the silicon source is fumed silica, aqueous colloidal silica, tetraethylorthosilicate, or mixtures thereof. S31. The method of Claim 15 wherein the crystalline solid is further subjected to washing with A K S 1 L/t 1 *r YIP llssuisr 41 and acid solution, a salt solution, an organic solvent or deionized water; drying; and thermal treatment.

32. A method as claimed in claim 15 substantially as hereinbefore described with reference to any one of the examples. DATED: 6 March 1991 PHILLIPS ORMONDE FITZPATRICK Attorneys for: THE DOW CHEMICAL COMPANY 0 0 a 0 S* S. I I 4