Synthesis of crystalline aluminophosphate composition

Abstract

This invention relates to a new crystalline aluminophosphate composition, to a new and useful improvement in synthesizing said crystalline composition and to use of said crystalline composition prepared in accordance herewith as a catalyst component for organic compound, e.g. hydrocarbon compound, conversion.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a new and useful improvement in synthesizing a crystalline aluminophosphate composition from a reaction mixture containing a specific new directing agent, hereinafter more particularly defined, the new crystalline composition synthesized, and to use of the crystalline composition synthesized in accordance herewith as a catalyst component for organic compound, e.g. hydrocarbon compound, conversion.

More particularly, this invention relates to an improved method for preparing a crystalline aluminophosphate composition whereby synthesis is facilitated and reproducible and the product comprises crystals having large pore windows measuring greater than about 10 Angstroms in diameter, such as, for example, greater than about 12 Angstroms in diameter.

2. Discussion of the Prior Art

Zeolitic materials, both natural and synthetic, have been demonstrated in the past to have catalytic properties for various types of hydrocarbon conversion. Certain zeolitic materials are ordered, porous crystalline aluminosilicates having a definite crystalline structure as determined by X-ray diffraction, within which there are a large number of smaller cavities which may be interconnected by a number of still smaller channels or pores. These cavities and pores are uniform in size within a specific zeolitic material. Since the dimensions of these pores are such as to accept for adsorption molecules of certain dimensions while rejecting those of larger dimensions, these materials have come to be known as "molecular sieves" and are utilized in a variety of ways to take advantage of these properties.

Such molecular sieves, both natural and synthetic, include a wide variety of positive ion-containing crystalline aluminosilicates. These aluminosilicates can be described as rigid three-dimensional frameworks of SiO.sub.4 and AlO.sub.4 in which the tetrahedra are cross-linked by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen atoms is 1:2. The electrovalence of the tetrahedra containing aluminum is balanced by the inclusion in the crystal of a cation, for example an alkali metal or an alkaline earth metal cation. This can be expressed wherein the ratio of aluminum to the number of various cations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity. One type of cation may be exchanged either entirely or partially with another type of cation utilizing ion exchange techniques in a conventional manner. By means of such cation exchange, it has been possible to vary the properties of a given aluminosilicate by suitable selection of the cation. The spaces between the tetrahedra are occupied by molecules of water prior to dehydration.

Prior art techniques have resulted in the formation of a great variety of synthetic zeolites. The zeolites have come to be designated by letter or other convenient symbols, as illustrated by zeolite A (U.S. Pat. No. 2,882,243), zeolite X (U.S. Pat. No. 2,882,244), zeolite Y (U.S. Pat. No. 3,130,007), zeolite ZK-5 (U.S. Pat. No. 3,247,195), zeolite ZK-4 (U.S. Pat. No. 3,314,752), zeolite ZSM-5 (U.S. Pat. No. 3,702,886), zeolite ZSM-11 (U.S. Pat. No. 3,709,979), zeolite ZSM-12 (U.S. Pat. No. 3,832,449), zeolite ZSM-20 (U.S. Pat. No. 3,972,983), zeolite ZSM-35 (U.S. Pat. No. 4,016,245), zeolite ZSM-38 (U.S. Pat. No. 4,046,859), and zeolite ZSM-23 (U.S. Pat. No. 4,076,842) merely to name a few.

Aluminum phosphates are taught in U.S. Pat. Nos. 4,310,440 and 4,385,994, for example. These aluminum phosphate materials have essentially electroneutral lattices. U.S. Pat. No. 3,801,704 teaches an aluminum phosphate treated in a certain way to impart acidity.

An early reference to a hydrated aluminum phosphate which is crystalline until heated at about 110.degree. C., at which point it becomes amorphous, is the "H.sub.1 " phase or hydrate of aluminum phosphate of F. d'Yvoire, Memoir Presented to the Chemical Society, No. 392, "Study of Aluminum Phosphate and Trivalent Iron", Jul. 6, 1961 (received), pp. 1762-1776. This material, when crystalline, is identified by the Joint Commission for Powder Diffraction Standards (JCPDS), card number 15-274, and has an X-ray diffraction pattern exhibiting lines of Tables 1A, 1B and 1C, hereinafter presented. Once heated at about 110.degree. C., however, the d'Yvoire material becomes amorphous.

Silicoaluminophosphates of various structures are taught in U.S. Pat. No. 4,440,871. Aluminosilicates containing phosphorous, i.e. silicoaluminophosphates of particular structures are taught in U.S. Pat. No. 3,355,246 (i.e. ZK-21) and U.S. Pat. No. 3,791,964 (i.e. ZK-22). Other teachings of silicoaluminophosphates and their synthesis include U.S. Pat. No. 4,673,559 (two-phase synthesis method); U.S. Pat. No. 4,623,527 (MCM-10); U.S. Pat. No. 4,639,358 (MCM-1); U.S. Pat. No. 4,647,442 (MCM-2); U.S. Pat. No. 4,664,897 (MCM-4); U.S. Pat. No. 4,639,357 (MCM-5) and U.S. Pat. No.4,632,811 (MCM-3).

A method for synthesizing crystalline metalloaluminophosphates is shown in U.S. Pat. No. 4,713,227 and an antimonophosphoaluminate is taught in U.S. Pat. No. 4,619,818. U.S. Pat. No. 4,567,029 teaches metalloaluminophosphates, and titaniumaluminophosphate is taught in U.S. Pat. No. 4,500,651.

The phosphorus-substituted zeolites of Canadian Patents 911,416; 911,417 and 911,418 are referred to as "aluminosilicophosphate" zeolites. Some of the phosphorus therein appears to be occluded, not structural.

U.S. Pat. No. 4,363,748 describes a combination of silica and aluminum-calcium-cerium phosphate as a low acid activity catalyst for oxidative dehydrogenation. Great Britain Patent 2,068,253 discloses a combination of silica and aluminum-calcium-tungsten phosphate as a low acid activity catalyst for oxidative dehydrogenation. U.S. Pat. No. 4,228,036 teaches an alumina-aluminum phosphate-silica matrix as an amorphous body to be mixed with zeolite for use as cracking catalyst. U.S. Pat. No. 3,213,035 teaches improving hardness of aluminosilicate catalysts by treatment with phosphoric acid. The catalysts are amorphous.

U.S. Pat. No. 2,876,266 describes an active silicophosphoric acid or salt phases of an amorphous material prepared by absorption of phosphoric acid by premolded silicates or aluminosilicates.

Other patents teaching aluminum phosphates include U.S. Pat. Nos. 4,365,095; 4,361,705; 4,222,896; 4,210,560; 4,179,358; 4,158,621; 4,071,471; 4,014,945; 3,904,550 and 3,697,550.

Lok et al. (Zeolites, 1983, vol. 3, Oct. 282-291) teach numerous organic compounds which act as directing agents for synthesis of various crystalline materials, such as, for example, ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-35, ZSM-48, AlPO.sub.4 -5, AlPO.sub.4 -8, AlPO.sub.4 -20 and others. The article does not shown use of the presently required directing agent compound for synthesis of the aluminophosphate composition of this invention. ZSM-5 and AlPO.sub.4 -5 are taught by Lok et al to be directed by tetrapropylammonium hydroxide from appropriate reaction mixtures. Choline compounds are taught to direct synthesis of ZSM-34, ZSM-38, ZSM-43, AlPO.sub.4 -5 and AlPO.sub.4 -7.

Other publications teaching various organic directing agents for synthesis of various crystalline materials include, for example, U.S. Pat. No. 4,592,902, teaching use of an alkyltropinium directing agent, alkyl being of 2 to 5 carbon atoms, for synthesis of ZSM-5; U.S. Pat. No. 4,640,829, teaching use of dibenzyldimethylammonium directing agent for synthesis of ZSM-50; U.S. Pat. No. 4,637,923, teaching use of (CH.sub.3).sub.2 (C.sub.2 H.sub.5)N.sup.+ (CH.sub.2).sub.4 N.sup.+ (C.sub.2 H.sub.5) (CH.sub.3).sub.2 directing agent for synthesis of a novel zeolite; U.S. Pat. No. 4,585,747, teaching use of bis (N-methylpyridyl) ethylinium directing agent for synthesis of ZSM-48; U.S. Pat. No. 4,585,746, teaching use of bis (N-methylpyridyl) ethylinium directing agent for synthesis of ZSM-12; U.S. Pat. No. 4,584,286, teaching use of bis (N-methylpyridyl) ethylinium directing agent for synthesis of ZSM-35; U.S. Pat. No. 4,568,654, teaching use of cobalticinium, dimethylpiperidinium, trimethylene bis trimethylammonium or tetramethylpiperazinium directing agents for synthesis of ZSM-51; U.S. Pat. No. 4,559,213, teaching use of DABCO-C.sub.4-10 -diquat directing agent for synthesis of ZSM-12; U.S. Pat. No. 4,482,531, teaching synthesis of ZSM-12 with a DABCO-C.sub.n -diquat, n being 4,5,6 or 10, directing agent; and U.S. Pat. No. 4,539,193, teaching use of bis (dimethylpiperidinium) trimethylene directing agent for synthesis of ZSM-12.

U.S. Pat. No. 4,139,600 teaches a method for synthesis of zeolite ZSM-5, having a structure different from the presently synthesized crystal, from a reaction mixture comprising, as a directing agent, an alkyldiamine. U.S. Pat. No. 4,296,083 claims synthesizing zeolites characterized by Constraint Index of 1 to 12 and an alumina/silica mole ratio of not greater than 0.083 from a specified reaction mixture containing an organic nitrogen-containing cation provided by an amine identified as being selected from the group consisting of triethylamine, trimethylamine, tripropylamine, ethylenediamine, propanediamine, butanediamine, pentanediamine, hexanediamine, methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, benzylamine, aniline, pyridine, piperidine and pyrrolidine.

U.S. Pat. No. 4,151,189 claims a method for synthesizing zeolites ZSM-5, ZSM-12, ZSM-35 and ZSM-38 containing an organic nitrogen cation from a specified reaction mixture containing a primary amine having 2 to 9 carbon atoms as a directing agent. U.S. Pat. No. 4,341,748 shows synthesis of ZSM-5 structure from reaction mixtures comprising ethanol, ZSM-5 seeds, ethanol and seeds, ethanol and ammonium hydroxide, and ethanol, ammonium hydroxide and ZSM-5 seeds. U.S. Pat. No. 4,100,262 teaches synthesis of ZSM-5 from a reaction mixture comprising a tetraalkylammonium source and a tetraureacobalt (II) complex.

Various diquaternary ammonium compounds have been identified as directing agents for a various assortment of crystalline materials. For instance, U.S. Pat. Nos. 4,490,342 and 4,619,820 show synthesis of ZSM-23 from a reaction mixture containing the organic of U.S. Pat. No. 4,531,012, i.e. (CH.sub.3).sub.3 N.sup.+ (R)N.sup.+ (CH.sub.3).sub.3, where R is a saturated or unsaturated hydrocarbon having 7 carbon atoms. U.S. Pat. No. 4,623,527 teaches numerous diquaternary ammonium compounds and shows use of (CH.sub.3).sub.3 N.sup.+ (CH.sub.2).sub.7 N.sup.+ (CH.sub.3).sub.3 directing agent for synthesis of MCM-10.

U.S. Pat. No. 4,632,815 teaches numerous diquaternary ammonium compounds and shows use of (CH.sub.3).sub.3 N.sup.+ (CH.sub.2).sub.4 N.sup.+ (CH.sub.3).sub.3 to direct synthesis of a Silica-X structure type. U.S. Pat. No. 4,585,639 teaches use of the diquaternary (C.sub.2 H.sub.5) (CH.sub.3).sub.2 N+(CH.sub.2).sub.4or6 N.sup.+ (CH.sub.3).sub.2 (C.sub.2 H.sub.5) as directing agent for synthesis of ZSM-12. Synthesis of ZSM-5 is directed by the diquaternary (alkyl).sub.3 N.sup.+ (CH.sub.2).sub.6 N.sup.+ (alkyl).sub.3, alkyl being propyl or butyl, in U.S. Pat. No. 4,585,638.

EPA 42,226 and U.S. Pat. No. 4,537,754 teach existence of numerous diquaternary ammonium compounds, but show use of (CH.sub.3).sub.3 N.sup.+ (CH.sub.2).sub.6 N.sup.+ (CH.sub.3).sub.3 as directing agent for synthesis of EU-1. EPA 51,318 teaches use of the same diquaternary for synthesis of TPZ-3. It is noted that EU-1, TPZ-3 and ZSM-50 have the same structure.

Applicants know of no prior art for preparing the crystalline aluminophosphate composition utilizing as a directing agent that required of the present invention.

SUMMARY OF THE INVENTION

An improved, economical and reproducible hydrothermal synthesis method for preparing crystalline aluminophosphate exhibiting valuable properties is provided. The method comprises forming a reaction mixture hydrogel containing sources of aluminum oxide, phosphorus oxide, directing agent, and water and having a composition, in terms of mole ratios, within the following ranges:

______________________________________ Broad Preferrred Most Preferred______________________________________P.sub.2 O.sub.5 /Al.sub.2 O.sub.3 0.5 to 1.27 0.9 to 1.1 0.9 to 1.1H.sub.2 O/Al.sub.2 O.sub.3 10 to 100 20 to 80 30 to 60DA/Al.sub.2 O.sub.3 0.2 to 0.8 0.3 to 0.7 0.4 to 0.6______________________________________ where DA is the directing agent, hereinafter more particularly defined, and maintaining the mixture until crystals of the desired crystalline composition are formed.

Reaction conditions required of the instant invention are critical and consist of heating the foregoing reaction mixture to a temperature of from about 100.degree. C. to less than about 160.degree. C. for a period of time of from about 1 hour to about 80 hours. A more preferred temperature range is from about 130.degree. C. to about 150.degree. C. with the amount of time at a temperature in such range being from about 10 hours to about 30 hours. If the temperature is about 160.degree. C. or more, the product composition will be diminished of desired large pore crystals characterized by the X-ray diffraction patterns of Tables 1A, 1B and 1C, hereinafter presented. Also critical of this synthesis procedure is the reaction mixture ratio of P.sub.2 O.sub.5 /Al.sub.2 O.sub.3. When the ratio P.sub.2 O.sub.5 /Al.sub.2 O.sub.3 is greater than about 1.27, especially when the temperature is 160.degree. C. or higher, product composition will be diminished of desired large pore crystals characterized by the X-ray diffraction patterns of Tables 1A, 1B and 1C, hereinafter presented.

The solid product composition comprising the desired aluminophosphate is recovered from the reaction medium, as by cooling the whole to room temperature, filtering and water washing.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the X-ray powder diffraction pattern of the product of Example 1.

FIG. 2 is the X-ray powder diffraction pattern of the product of Example 2.

FIG. 3 is the X-ray powder diffraction pattern of the product of Example 3.

FIG. 4 is the X-ray powder diffraction pattern of the product of Example 4.

EMBODIMENTS

The crystalline aluminophosphate composition synthesized in accordance with the present method exhibits utility as a catalyst component for certain chemical reactions of interest, including cracking, hydrocracking, disproportionation, alkylation, isomerization and oxidation.

The particular effectiveness of the presently required directing agent, when compared with other directing agents, such as those identified above, is believed due to its ability to function as a template in the above reaction mixture in the nucleation and growth of the desired aluminophosphate crystals with the limitations above discussed. This directing agent is the compound represented by the formula: ##STR1## wherein X is an ion such as one selected from the group consisting of hydroxide and halide (e.g. chloride or bromide), and R, R', R" and R'" are the same or different and are selected from the group consisting of --CH.sub.2 X and --CH.sub.2 CH.sub.2 X. Non-limiting examples of these compounds include tetrakis (2-hydroxyethyl)ammonium hydroxide, tetrakis (2-chloroethyl)ammonium chloride and tetrakis (hydroxymethyl)ammonium bromide.

The synthesis of the present invention may be facilitated when the reaction mixture comprises seed crystals, such as those having the structure of the product crystals. The use of at least 0.01%, preferably about 0.10%, and even more preferably about 1% seed crystals (based on total weight) of crystalline material in the reaction mixture will facilitate crystallization in the present method.

The reaction mixture composition for the synthesis of synthetic crystalline aluminophosphate hereby can be prepared utilizing materials which can supply the appropriate oxide. The useful sources of aluminum oxide include, as non-limiting examples, any known form of aluminum oxide or hydroxide, organic or inorganic salt or compound, e.g. alumina and aluminates. Such sources of aluminum oxide include pseudo-boehmite and aluminum tetraalkoxide. The useful sources of phosphorus oxide include, as non-limiting examples, any known form of phosphorus acids or phosphorus oxides, phosphates and phosphites, and organic derivatives of phosphorus.

It will be understood that each oxide component utilized in the reaction mixture for preparing the present crystalline composition can be supplied by one or more essential reactants and they can be mixed together in any order. For example, any oxide can be supplied by an aqueous solution. The reaction mixture can be prepared either batchwise or continuously. Crystal size and crystallization time for the product composition comprising the desired aluminophosphate will vary with the exact nature of the reaction mixture employed within the above-described limitations.

The present product composition as synthesized hereby can be identified, in terms of mole ratios of oxides as follows:

mA.sub.2 O:Al.sub.2 O.sub.3 :xP.sub.2 O.sub.5 :nH.sub.2 O wherein A represents the anion portion of the directing agent compound used in synthesis of the product composition, m is a number of from 0 (e.g. about 0.2) to about 0.8, x is a number of from about 0.5 to about 1.5, and n is a number of from 0 (e.g. less than about 10) to about 100. Any organic material resulting from directing agent used in the synthesis procedure may be removed upon calcination.

The composition resulting from the present method comprises crystals having a framework topology which exhibit, even after being heated at 110.degree. C. or higher, a characteristic X-ray diffraction pattern having the following characteristic values:

TABLE 1A______________________________________Interplanar d-Spacings (A) Relative Intensity______________________________________16.4 .+-. 0.2 vs8.2 .+-. 0.1 w4.74 .+-. 0.05 w______________________________________ and more specifically the following characteristic values: TABLE 1B______________________________________Interplanar d-Spacings (A) Relative Intensity______________________________________ 16.4 .+-. 0.2 vs 8.2 .+-. 0.1 w 6.21 .+-. 0.05 w 6.17 5.48 .+-. 0.05 w 4.74 .+-. 0.05 w______________________________________ and even more specifically the following characteristic values: TABLE 1C______________________________________Interplanar d-Spacings (A) Relative Intensity______________________________________ 16.4 .+-. 0.2 vs 8.2 .+-. 0.1 w 6.21 .+-. 0.05 w 6.17 5.48 .+-. 0.05 w 4.74 .+-. 0.05 w 4.10 .+-. 0.04 w 4.05 .+-. 0.04 w 3.96 .+-. 0.04 w 3.94 3.76 .+-. 0.03 w 3.28 .+-. 0.03 w______________________________________

The X-ray diffraction lines in Tables 1A, 1B and 1C identify a crystal framework topology in the composition exhibiting large pore windows of 18-membered ring size. The pores are at least about 10 Angstroms in diameter, such as for example at least about 12 Angstroms, e.g. 12-13 Angstroms, in diameter. These lines distinguish this topology from other crystalline aluminosilicate, aluminophosphate and silicoaluminophosphate structures. It is noted that the X-ray pattern of the present composition is void of a d-spacing value at 13.6-13.3 Angstroms with any significant intensity relative the strongest d-spacing value. If a d-spacing value in this range appears in a sample of the present composition, it is due to impurity and will have a weak relative intensity. An 18-membered ring structure was published by M. Davis, D. Saldarriaga, C. Montes and J. Garces at the "Innovation in Zeolite Materials Science" meeting in Nieuwpoort, Belgium, Sep. 13-17, 1987. The large pore "AlPO.sub.4 -8" of U.S. Pat. No. 4,310,440 had a d-spacing value at 13.6-13.3 Angstroms with a medium-very strong relative intensity as reported in the patent. The d'Yvoire aluminum phosphate identified above, i.e. JCPDS card number 15-274, is not crystalline after being heated at about 110.degree. C.

These X-ray diffraction data were collected with conventional X-ray systems, using copper K-alpha radiation. The positions of the peaks, expressed in degrees 2 theta, where theta is the Bragg angle, were determined by scanning 2 theta. The interplanar spacings, d, measured in Angstrom units (A), and the relative intensities of the lines, I/I.sub.o, where I.sub.o is one-hundredth of the intensity of the strongest line, including subtraction of the background, were derived. The relative intensities are given in terms of the symbols vs=very strong (75-100%), s=strong (50-74%), m=medium (25-49%) and w=weak (0-24%). It should be understood that this X-ray diffraction pattern is characteristic of all the species of the present compositions. Ion exchange of cations with other ions results in a composition which reveals substantially the same X-ray diffraction pattern with some minor shifts in interplanar spacing and variation in relative intensity. Relative intensity of individual lines may also vary relative the strongest line when the composition is chemically treated, such as by dilute acid treatment. Other variations can occur, depending on the composition component ratios of the particular sample, as well as its degree of thermal treatment. The relative intensities of the lines are also susceptible to changes by factors such as sorption of water, hydrocarbons or other components in the channel structure. Further, the optics of the X-ray diffraction equipment can have significant effects on intensity, particularly in the low angle region. Intensities may also be affected by preferred crystallite orientation.

While the improved crystalline composition of the present invention may be used as a catalyst component in a wide variety of organic compound, e.g. hydrocarbon compound, conversion reactions, it is notably useful in the processes of cracking, hydrocracking, isomerization and reforming. Other conversion processes for which the present composition may be utilized as a catalyst component include, for example, dewaxing.

The present composition, when employed either as an adsorbent or as a catalyst component in a hydrocarbon conversion process, should be dehydrated at least partially. This can be done by heating to a temperature in the range of from about 65.degree. C. to about 315.degree. C. in an inert atmosphere, such as air, nitrogen, etc. and at atmospheric or subatmospheric pressures for between 1 and 48 hours. Dehydration can be performed at lower temperature merely by placing the zeolite in a vacuum, but a longer time is required to obtain a particular degree of dehydration. The thermal decomposition product of the newly synthesized composition can be prepared by heating same at a temperature of from about 200.degree. C. to about 550.degree. C. for from 1 hour to about 48 hours.

The composition prepared by the instant invention may be formed in a wide variety of particle sizes. Generally speaking, the particles can be in the form of a powder, a granule, or a molded product, such as extrudate having particle size sufficient to pass through a 2 mesh (Tyler) screen and be retained on a 400 mesh (Tyler) screen. In cases where the catalyst comprising the present material is molded, such as by extrusion, the material can be extruded before drying or dried or partially dried and then extruded.

In the case of many catalysts, it may be desired to incorporate the hereby prepared aluminophosphate with another material resistant to the temperatures and other conditions employed in certain organic conversion processes. Such matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as incorganic materials such as clays, silica and/or metal oxides, e.g. alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates, sols or gels including mixtures of silica and metal oxides. Use of a material in conjunction with the present aluminophosphate, i.e. combined therewith, which is active, may enhance the conversion and/or selectivity of the catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate or reaction. Frequently, crystalline catalytic materials have been incorporated into naturally occurring clays, e.g. bentonite and kaolin. These materials, i.e. clays, oxides, etc., function, in part, as binders for the catalyst. It is desirable to provide a catalyst having good crush strength, because in a petroleum refinery the catalyst is often subjected to rough handling, which tends to break the catalyst down into powder-like materials which cause problems in processing.

Naturally occurring clays which can be composited with the hereby synthesized aluminophosphate include the montmorillonite and kaolin families which include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays, or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.

In addition to the foregoing materials, the crystals hereby synthesized can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in the form of a cogel. A mixture of these components could also be used.

The relative proportions of finely divided crystalline material and matrix vary widely with the crystalline material content ranging from about 1 to about 90 percent by weight, and more usually in the range of about 2 to about 50 percent by weight of the composite.

Employing a catalyst comprising the composition of this invention containing a hydrogenation component, reforming stocks can be reformed employing a temperature between 450.degree. C. and 550.degree. C. The pressure can be between 50 and 500 psig, but is preferably between 100 and 300 psig. The liquid hourly space velocity is generally between 0.1 and 10 hr.sup.-1, preferably between 1 and 4 hr.sup.-1 and the hydrogen to hydrocarbon mole ratio is generally between 1 and 10, preferably between 3 and 5.

A catalyst comprising the present composition can also be used for hydroisomerization of normal paraffins, when provided with a hydrogenation component, e.g. platinum. Hydroisomerization is carried out at a temperature between 250.degree. C. to 450.degree. C., preferably 300.degree. C. to 425.degree. C., with a liquid hourly space velocity between 0.1 and 10 hr.sup.-1, preferably between 0.5 and 4 hr.sup.-1, employing hydrogen such that the hydrogen to hydrocarbon mole ratio is between 1 and 10. Additionally, the catalyst can be used for olefin or aromatics isomerization employing temperatures between 0.degree. C. and 550.degree. C.

A catalyst comprising the aluminophosphate of this invention can also be used for reducing the pour point of gas oils. This process is carried out at a liquid hourly space velocity between about 0.1 and about 5 hr.sup.-1 and a temperature between about 300.degree. C. and about 425.degree. C.

Other reactions which can be accomplished employing a catalyst comprising the composition of this invention containing a metal, e.g. platinum, include hydrogenation-dehydrogenation reactions and desulfurization reactions, olefin polymerization (oligomerization), and other organic compound conversions such as the conversion of alcohols (e.g. methanol) to hydrocarbons.

In order to more fully illustrate the nature of the invention and the manner of practicing same, the following examples are presented.

EXAMPLE 1

A mixture containing 103.5 g of 85% orthophosphoric acid (H.sub.3 PO.sub.4) in 155 g water was mixed with 50.8 g aluminum oxide source (pseudo-boehmite). The mixture was heated to 80.degree. C. with stirring for 1 hour. To this mixture was added 105.5 g tetrakis (2-hydroxyethyl) ammonium hydroxide (DA) in 150 g water, giving a final reaction mixture composed as follows:

______________________________________ P.sub.2 O.sub.5 /Al.sub.2 O.sub.3 = 1.26 H.sub.2 O/Al.sub.2 O.sub.3 = 52 DA/Al.sub.2 O.sub.3 = 0.7______________________________________

The reaction mixture was placed in a 1000 cc autocalve. Crystallization in the autoclave was at 140.degree. C. under 300 psig nitrogen for 16 hours. The solid product was filtered, washed and dried. Washing was accomplished by extraction with water in a Soxhlet apparatus. The product was calcined at 538.degree. C. in air for 10 hours.

The calcined product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 2 and FIG. 1.

TABLE 2______________________________________Interplanar Observed Relatived-Spacings (A) 2 .times. Theta Intensities (I/I.sub.o)______________________________________19.62633 4.502 2.016.50637 5.354 100.011.95308 7.396 7.18.24634 10.728 27.26.20381 14.277 12.94.74095 18.717 12.74.33935 20.467 1.44.19087 21.200 4.54.08690 21.746 57.14.06799 21.848 67.23.96914 22.399 42.03.95098 22.504 46.03.79405 23.447 13.33.77009 23.598 24.33.58563 24.831 5.73.50222 25.433 0.43.47553 25.631 1.43.43484 25.940 2.23.41076 26.126 1.03.28214 27.169 32.23.17008 28.149 4.93.15501 28.287 4.43.08670 28.926 14.23.08117 28.979 11.13.03351 29.445 2.32.95461 30.249 9.22.95086 30.289 10.42.91456 30.675 1.42.81518 31.786 0.92.73786 32.709 12.72.73145 32.788 7.4______________________________________

Chemical analysis of the extracted Example 1 product indicated the following composition:

______________________________________ Al 19.63 wt. % P 21.04 wt. % Si 0.026 wt. % Na 0.029 wt. %______________________________________

EXAMPLE 2

A mixture containing 115 g of 85% orthophosphoric acid (H.sub.3 PO.sub.4) in 155 g water was mixed with 71 g aluminum oxide source (pseudo-boehmite). The mixture was heated to 80.degree. C. with stirring for 3 hours. To this mixture was added 105.5 g tetrakis(2-hydroxyethyl)ammonium hydroxide (DA) in 150 g water, giving a final reaction mixture composed as follows:

______________________________________ P.sub.2 O.sub.5 /Al.sub.2 O.sub.3 = 1 H.sub.2 O/Al.sub.2 O.sub.3 = 40 DA/Al.sub.2 O.sub.3 = 0.5______________________________________

The reaction mixture was placed in a 1000 cc autoclave. Crystallization in the autoclave was at 142.degree. C. under 300 psig nitrogen for 17 hours. The solid product was filtered, washed and dried. Washing was accomplished by extraction with water in a Soxhlet apparatus. The product as calcined at 530.degree. C. in air for 10 hours.

The calcined product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 3 and FIG. 2.

TABLE 3______________________________________Interplanar Observed Relatived-Spacings (A) 2 .times. Theta Intensities (I/I.sub.o)______________________________________16.57941 5.330 75.616.43716 5.376 100.08.21396 10.771 23.96.16367 14.370 13.94.73769 18.730 12.84.09134 21.722 45.64.05906 21.897 56.63.96168 22.442 30.83.93658 22.587 34.63.77338 23.578 18.33.42679 26.002 1.93.28000 27.188 30.33.19718 27.906 1.13.16223 28.221 5.33.07912 28.999 12.32.95194 30.277 10.72.94785 30.320 12.12.89369 30.902 3.22.73464 32.748 13.52.58822 34.658 0.6______________________________________

Chemical analysis of the extracted Example 2 product indicated the following composition:

______________________________________ Al 19.46 wt. % P 16.63 wt. % Si 0.046 wt. % Na 0.033 wt. %______________________________________

EXAMPLE 3

A mixture containing 57.5 g of 85% orthophosphoric acid (H.sub.3 PO.sub.4) in 77.5 g water was mixed with 35.5 g aluminum oxide source (pseudo-boehmite). The mixture was heated to 80.degree. C. with stirring for 1 hour. To this mixture was added 52.75 g tetrakis(2-hydroxyethyl)ammonium hydroxide (DA) in 75 g water, giving a final reaction mixture composed as follows:

______________________________________ P.sub.2 O.sub.5 /Al.sub.2 O.sub.3 = 1 H.sub.2 O/Al.sub.2 O.sub.3 = 41 DA/Al.sub.2 O.sub.3 = 0.5______________________________________

The reaction mixture was placed in an autoclave. Crystallization in the autoclave was at 138.degree. C. under 300 psig nitrogen for 14 hours. The solid product was filtered, washed and dried. Washing was accomplished by extraction with water in a Soxhlet apparatus. The product was calcined at 530.degree. C. in air for 10 hours.

The calcined product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 4 and FIG. 3.

TABLE 4______________________________________Interplanar Observed Relatived-Spacings (A) 2 .times. Theta Intensities (I/I.sub.o)______________________________________16.33147 5.411 100.08.19161 10.800 24.46.15847 14.382 13.74.73260 18.750 13.54.46994 19.863 1.14.07984 21.784 54.74.05933 21.895 61.43.95056 22.506 38.33.93839 22.576 39.43.77224 23.585 16.93.76217 23.649 23.53.62809 24.536 8.93.58473 24.838 8.03.27475 27.232 34.83.16219 28.221 8.43.07736 29.016 14.93.02653 29.514 8.72.94680 30.331 16.92.89666 30.869 8.42.88632 30.983 9.22.74261 32.650 11.02.73319 32.766 12.42.72987 32.807 9.7______________________________________

Chemical analysis of the extracted Example 3 product indicated the following composition:

______________________________________ Al 21.33 wt. % P 20.13 wt. % Si 0.028 wt. % Na 0.021 wt. %______________________________________

A mixture containing 61.5 g of 85% orthophosphoric acid (H.sub.3 PO.sub.4) in 92.1 g water was mixed with 30.2 g aluminum oxide source (pseudo-boehmite). The mixture was heated to 80.degree. C. with stirring for 1 hour. To this mixture was added 62.7 g tetrakis(2-hydroxyethyl)ammonium hydroxide (DA) in 89.2 g water, giving a final reaction mixture composed as follows:

______________________________________ P.sub.2 O.sub.5 /Al.sub.2 O.sub.3 = 1.28 H.sub.2 O/Al.sub.2 O.sub.3 = 52 DA/Al.sub.2 O.sub.3 = 0.71______________________________________

The reaction mixture was placed in an autoclave. Crystallization in the autoclave was at 160.degree. C. under 300 psig nitrogen for 5 hours. The solid product was filtered, washed with water and dried.

The product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 5 and FIG. 4.

TABLE 5______________________________________Interplanar Observed Relatived-Spacings (A) 2 .times. Theta Intensities (I/I.sub.o)______________________________________11.83947 7.467 56.46.83277 12.957 9.25.91531 14.977 23.94.46975 19.863 57.54.23470 20.978 47.93.94108 22.561 56.73.95335 22.490 100.03.59716 24.750 5.13.41379 26.103 36.83.30072 27.014 0.03.07036 29.083 13.33.06515 29.134 11.72.95580 30.237 21.42.65608 33.746 5.02.58051 34.765 17.1______________________________________

The product of Example 4, crystallized from the indicated reaction mixture at 160.degree. C. was found to be primarily AlPO.sub.4 -5, void of any significant amount of the large pore aluminophosphate crystals of the present synthesis invention.

Claims

1. A method for synthesizing an aluminophosphate composition comprising crystals having a framework topology after heating at 110.degree. C. or higher giving an X-ray diffraction pattern with lines shown in Table IA of the specification, which comprises (i) preparing a mixture capable of forming said composition, said mixture comprising sources of an oxide of aluminum, an oxide of phosphorus, water and a directing agent (DA), and having a composition, in terms of mole ratios, within the following ranges:

______________________________________P.sub.2 O.sub.5 /Al.sub.2 O.sub.3 0.5 to 1.27H.sub.2 O/Al.sub.2 O.sub.3 10 to 100DA/Al.sub.2 O.sub.3 0.2 to 0.8______________________________________

wherein DA is a tetrakis(2-hydroxyethyl) ammonium compound, (ii) maintaining said mixture under sufficient conditions including a temperature of from about 100.degree. C. to less than about 160.degree. C. until crystals of said composition are formed and (iii) recovering said crystalline aluminophosphate composition from step (ii) having a formula in terms of mole ratios of oxides mA.sub.2 O:Al.sub.2 O.sub.3 :xP.sub.2 O.sub.5 :nH.sub.2 O, wherein A represents the cation portion of DA, m is a number from about 0.2 to about 0.8, x is a number from about 0.5 to about 1.5, and n is a number from 0 to 100.

2. The method of claim 1 wherein said mixtures has the following composition ranges:

______________________________________P.sub.2 O.sub.5 /Al.sub.2 O.sub.3 0.9 to 1.1H.sub.2 O/Al.sub.2 O.sub.3 20 to 80DA/Al.sub.2 O.sub.3 0.3 to 0.7______________________________________

3. The method of claim 1 wherein said crystals give an X-ray diffraction pattern with lines shown in Table 1B.

4. The method of claim 1 wherein said crystals give an X-ray diffraction pattern with lines shown in Table 1C.

5. The method of claim 1 wherein said mixture further comprises seed crystals in sufficient amount to enhance synthesis of said crystalline aluminophosphate.

6. The method of claim 2 wherein said crystals given an X-ray diffraction pattern with lines shown in Table 1B.

7. The method of claim 2 wherein said crystals give an X-ray diffraction pattern with lines shown in Table 1C.

8. The recovered crystalline aluminophosphate composition of claim 1.

9. The recovered crystalline aluminophosphate composition of claim 2.

10. A crystalline aluminophosphate composition comprising crystals which exhibit an X-ray diffraction pattern having values of Table 1A and contain an ion of the formula: ##STR2## wherein R, R', R" and R"' are the same or different and are selected from the group consisting of --CH.sub.2 X and --CH.sub.2 CH.sub.2 X, X being hydroxide or halide.

11. A crystalline aluminophosphate composition comprising crystals which exhibit an X-ray diffraction pattern having values of Table 1B and contain an ion of the formula: ##STR3## wherein R, R', R" and R"' are the same or different and are selected from the group consisting of --CH.sub.2 X and --CH.sub.2 CH.sub.2 X, X being hydroxide or halide.

12. A crystalline aluminophosphate composition comprising crystals which exhibit an X-ray diffraction pattern having values of Table 1C and contain an ion of the formula: ##STR4## wherein R, R', R" and R"' are the same or different and are selected from the group consisting of --CH.sub.2 X and --CH.sub.2 CH.sub.2 X, X being hydroxide or halide.

13. A catalyst composition comprising the crystalline aluminophosphate of claim 8 and a catalytically active or inactive component.

14. A catalyst composition comprising the crystalline aluminophosphate of claim 10 and a catalytically active or inactive component.