JPH0574523B2 - - Google Patents

Description

Claim 1: It has a three-dimensional microporous crystal skeleton structure, has a chemical composition expressed by a molar ratio of oxides of Al ₂ O ₃ :1.0±0.2P ₂ O ₅ , and is produced using CuK-α rays. When measured with
A crystalline aluminum phosphate composition defined as having an X-ray powder diffraction pattern characterized by a d-spacing of 2 to 17 Å at 2θ less than 40°. 2 has a three-dimensional microporous crystalline structure such that the chemical composition of the precursor mixture expressed in molar ratio of oxides is _Al2O3 : _1.0 ± _0.2P2O5 : ₁₀ ~ _100H2O ; A method for producing a crystalline aluminum phosphate composition comprising 0.02 to 4.0 moles of structural director for each mole of Al ₂ O ₃ , comprising: (1) mixing an aluminum source, a phosphorus source, and water to form a precursor mixture; (2) combining the precursor mixture and a structure-directing agent to form a reaction mixture; and (3) the crystalline solid having a 2θ of less than about 40° as measured using CuK-α radiation. heating said reaction mixture at from 50<0>C to 200[deg.]C in conditions such that it has an X-ray powder diffraction pattern characterized by a d-spacing of 2 to 17 Å. Description The present invention relates to crystalline aluminum phosphate compositions, and more particularly to large pore crystalline aluminum phosphate compositions and methods of making the same. Molecular sieves have been well known in the art for many years. Generally, these are of two types;
Zeolite type consisting of crystalline aluminosilicate molecular sieves and other molecular sieves that are not composed of crystalline aluminosilicate compositions. Naturally occurring and synthetic analogs of zeolites are 100
Contains compositions exceeding . Zeolites are by definition tectosilicates, meaning that their framework is a three-dimensional structure consisting of SiO ₄ ^-4 and AlO ₄ ^-5 tetrahedra sharing vertices with oxygen atoms.
Zeolites have a porous structure with openings of uniform size; they are characterized by their ion exchange capacity; and the ability to reversibly adsorb and desorb molecules through the openings into the interstices present in the crystals. . These pore openings are defined by the bonding of TO ₄ tetrahedra, where T represents either a silicon or aluminum atom. Zeolites are generally synthesized by hydrothermal methods from reaction components in a closed system. A large catalog of empirical data on synthetic compositions and conditions leading to a given zeolite formation is available in the literature. Practice shows that different zeolite products can be obtained from the same starting material, depending on the raw materials, mixing methods and crystallization means used. Other crystalline molecular sieves that are not zeolites are also well known. Silica polymorphs have been awarded a U.S. patent
4061712, which exhibits molecular sieve properties but lacks cation exchange ability. Crystalline aluminum phosphates with molecular sieve properties representing a new class of adsorbents are described in US Pat. No. 4,310,440. The properties of these aluminum phosphates are somewhat similar to zeolite-based molecular sieves;
They are therefore useful as catalytic bases or catalysts in a variety of chemical reactions. US Patent No.
4440871 and European Patent Application No. 014638 describe crystalline silicoaluminum phosphates having similar molecular sieve, ion exchange and catalytic properties to zeolite and/or aluminum phosphate molecular sieves. Molecular sieve, ion exchange and catalytic properties similar to those of zeolites have also been found in certain metallosilicates. Instead of silicon or aluminum, it contains beryllium, boron, gallium,
It uses elements such as iron, titanium and phosphorous. These are E. Moretsutei et al. (E.
Zeolite Synthesis in the Presence of Organic Components (Moretti et.al.)
Presence of Organic Components)”KIMICA
Chimica e
Industria), 67 (1985) 21-34. However, all of the crystalline substances mentioned above are approximately
It is known to have closed pores ranging from 2.1 to about 7.4 Å. The largest pore appears to be defined by a ring of 12 TO ₄ tetrahedra. To date, although there have been reports of the synthesis of non-zeolitic molecular sieve compositions with larger pores, these reports have not been substantiated. For example, U.S. Pat.
No. 4,310,440 describes an aluminum phosphate composition referred to as AlPO ₄ -8 (an example of that patent).
62-A), which is perfluorotributylamine, PFTBA [(C ₄ F ₉ ) ₃ N)]
It has been reported that it adsorbs a considerable amount of PFTBA is known to have a kinetic diameter of approximately 10A. R.M. See RM Barrer, Zeolites and Clay Minerals (1978) 7.
Similar claims are made in British Patent No. 1394163 regarding a zeolite referred to as AG-4. However, none of these literatures conclusively determines whether PFTBA molecules are adsorbed by themselves into micropores, into hair-like pores between crystalline particles, or perhaps impurities that are either crystalline or amorphous. does not provide enough data to make a decision. Other materials reported to have large pores are Z-21, described in US Pat. No. 3,567,372, and zeolite N, similar to Z-21, described in US Pat. No. 3,414,602. More recently, Russian engineers have made claims for large-pore zeolites based on X-ray powder diffraction data (“Neorganicheskie Materiali”).
Materialy）”Izuvestiya Academy Nook SSS
Akademii Nauk SSSR) 17, 6 (June 1981)
1018-1021]. Therefore, herein, a crystalline aluminum phosphate composition having a three-dimensional microporous crystal skeleton structure, whose chemical composition expressed by the molar ratio of its oxides is Al ₂ O ₃ :1.0±0.2P. ₂ O ₅ and further as substantially shown in Table 1
Provided are those defined as having an X-ray powder diffraction pattern characterized by a d-spacing at 2θ of less than about 40° when measured using CuK-α radiation. The present invention further provides a structure-directing agent (structure-directing agent).
The present invention provides a crystalline aluminum phosphate composition having a three-dimensional microporous crystalline structure containing a directing agent), the chemical composition expressed in molar ratio being XR:Al ₂ O ₃ : 1.0±0.2P ₂ O ₅ , where Al ₂ O ₃ and P ₂ O ₅ form an oxide lattice; R represents a structural director; and X>0
; its structure is further substantially as shown in Table 1 when measured using CuK-α radiation.
X characterized by d-spacing in 2θ less than 40°
Defined as having a line powder diffraction pattern. The present invention also provides a method for preparing these crystalline aluminum phosphate compositions, which method has a chemical composition expressed in molar ratio of Al ₂ O ₃ :1.0±0.2P ₂ O ₅ :10. −100H ₂ O and for each mole of Al ₂ O ₃ a structural director
From a precursor mixture that is between 0.02 and 4.0 moles, an aluminum source, a phosphorus source, and water are combined into a precursor mixture, and the precursor mixture and a structural director are combined to form a reaction mixture, e.g. 1
The reaction mixture is subjected to conditions such that a crystalline aluminum phosphate composition is formed characterized by a d-spacing in 2θ of less than about 40° as measured using CuK-α radiation as shown in the table. It consists of reacting. The present invention further provides a crystalline metal-substituted aluminum phosphate composition having a three-dimensional microporous crystal skeleton structure containing a structural directing agent, the chemical composition expressed in molar ratio being XR: Al ₂ O ₃ : 1.0±. 0.2P ₂ O ₅ : 0.01−
0.5MOz/ ₂ : _{10-100H2O ,} where _{Al2O3 , P2O5} and MOz/ ₂ form an oxide lattice; R is a structural director; X>0
M is a metal; Z is the oxidation state of M; MOz/ ₂ is at least one metal oxide; the chemical composition further has one or more charge compensating species; the structure further comprises Defined as having an X-ray powder diffraction pattern characterized by a d-spacing in 2θ of less than about 40° when measured with CuK-α radiation substantially as shown in Table 1. It provides: Finally, the present invention provides a method for preparing these crystalline metal-substituted aluminum phosphate compositions, which method has a chemical composition expressed in molar ratios of Al ₂ O ₃ :1.0±0.5P. ₂ O ₅ : 0.001−
0.5MOz/ ₂ : _10-100H2O , where M is a metal; Z is the oxidation state of M; MOz/ ₂ is at least one metal oxide; the chemical composition is one or more further from a precursor composition containing a _charge -correcting _species of forming a precursor mixture, combining the precursor mixture and a structure-directing agent to form a reaction mixture, and forming a CuK-
d at 2θ less than about 40° when measured using alpha radiation
The method consists of reacting the reaction mixture under conditions such that a crystalline metal-substituted aluminum phosphate composition characterized by a spacing is formed. FIG. 1 shows argon adsorption isotherms for the aluminum phosphate of the present invention, designated "VPI-5", and zeolite X(Na) used for comparison purposes. Zeolite X(Na) has a US patent no.
Described in No. 2882244. FIG. 2 shows the effective pore size (Angstroms) for the aluminum phosphate of the invention and zeolite X(Na), designated VPI-5. The composition of one embodiment of the present invention is a synthetic crystalline aluminum phosphate material, hereinafter "VPI-
5'', which can reversibly adsorb and desorb large molecules such as triisopropylbenzene into intramolecular crystal pores. These substances consist of a three-dimensional microporous crystal skeleton structure. These aluminum phosphate materials are characterized in a number of ways.Generally, the basic chemical composition of the molecular sieve, expressed _in molar ratios, is _{Al2O3 :} 1.0± _0.2P2O5 ; has a crystal structure defined by an X-ray powder diffraction pattern having d-spacings substantially as given in Table 1. As used herein, the term "substantially" This means that the given d-spacings are within the tolerance for experimental error and therefore account for differences due to variations in equipment and technique. Shows characteristic d-spacings of VPI-5 between about 3° 2θ and about 40° 2θ when measured. “Characteristic” and “distinctive” as used herein mean that these d-spacings are about 10 It represents all peaks with an intensity related to the largest peak that is equal or greater.These peaks are labeled “Vs” for very strong ones.
or medium is indicated as having an intensity labeled "m". Lower intensity peaks are described as having weak (w) intensity and are therefore excluded from this definition. The d interval is
remains nearly the same even after heating the VPI-5 sample to at least about 600°C. This heating takes place, for example, in air or in an air/steam mixture under reduced pressure. The experimental X-ray diffraction patterns were obtained in an automatic powder diffractometer using CuK-α radiation.

【table】

[Table] Another property of the aluminum phosphate of the present invention is characterized by the d-spacing of the X-ray powder diffraction pattern, substantially as shown in Table 1, and based on these compositions, the XR : _Al2O3 :1.0 _{± 0.2P2O5} , where R is _the structure directing agent used in the synthesis of large pore materials and X is the molar ratio value of R to _{Al2O3 .} , X>0. Since the structure directing agent is part of the preparation process as discussed below, its amount in the composition depends somewhat on whether it undergoes partial desorption or degradation. In FIG. 1, argon adsorption isotherms of the VPI-5 aluminum phosphate of the present invention and zeolite X(Na) described in US Pat. No. 2,882,244 are shown. These results were obtained using an Omnisorp ^* 360 instrument (*Omnisorp is a product of Omicron Technology Corporation) at liquid argon temperatures.
A registered trademark of Omicron Technology Corporation. ) was measured. Figure 2 shows the effective pore size for VPI-5 and US Pat. No. 2,882,244 zeolites. Adsorption isotherms and pore size distributions were determined using the Horvath-Kawazoe analysis method (G. Horvath et al., “Method of Effect Pore Size Distribution in Molecular Sieve Carbon”).
Method for the calculation of effectiveness
Pore Size Distribution in Molecular Sieve
Carbon”, J.Chem, Eng. of Japan 16, (5)470−
475 (1983)). Zeolite X
(Na) is a typical example of a horujasite structure with a pore opening defined by a 12-membered ring tetrahedron, the allowable diameter of which is approximately 0.8 nm. This diameter is the second
Good agreement with the values shown in the figure. It has been demonstrated that VPI-5 has substantially larger pores than Zeolite X(Na). Therefore, it can be deduced from the above experiments that the VPI-5 composition exhibits a crystalline structure with a pore system such that some of its pore spacings are large enough to allow entry and exit of molecules of triisopropylbenzene. . Other pore spacings are available for smaller molecules. Metal-substituted aluminum phosphates were also characterized through X-ray diffraction. The observed powder pattern exhibits the same distinctive d-spacing as that obtained with unsubstituted VPI-5 as shown in Table 1. These metal _- substituted aluminum phosphates are _P2O5
shows a similar molar ratio of Al ₂ O ₃ to . Generally these compositions _are defined by the following molar ratio: _Al2O3 :1.0 _{± 0.2P2O5} :0.01−0.5MOz/
₂ : _10-100H2O In this formula M is a metal, Z is the acid value state of M, and MOz/ ₂ is at least one metal oxide. For example, the formula for the molar ratio of a silicoaluminum phosphate composition is _Al2O3 : _1.0 ± _0.2P2O5 : _{0.001−0.5SiO2 :}
The 10-100H ₂ O structure directing agent is present in the same proportions for the metal-substituted aluminum phosphate composition as for the unsubstituted aluminum phosphate composition, and the same selections as the aluminum and phosphorus sources and the structure directing agent are appropriate. Probably. Similarly, the structural directing agent is
Depending on whether desorption or decomposition has occurred,
The final silicoaluminum phosphate VPI-5 may or may not remain in the composition. Additionally, the chemical composition includes one or more species that provide charge correction to the metal-substituted aluminum phosphate species, thereby balancing the charges. These charge correction species include, for example, sodium, potassium, hydroxide,
A variety of cations or anions can be selected, such as chloride, and are known to those skilled in the art. Other elements from sources capable of forming oxides may also be substituted into the basic VPI-5 aluminum phosphate crystal framework structure without significantly affecting the X-ray powder diffraction pattern or the general oxide lattice structure. can. These include substituted metals such as titanium, tin, cobalt, zinc, magnesium, zirconium and mixtures thereof. The invention also comprises a method for preparing the VPI-5 compositions described herein. In general, the specific molar ratios of the reactant components are important in obtaining the final crystalline solid in accordance with the characteristic data described above. In summary, the crystalline aluminum phosphate of the present invention is prepared by combining an aluminum source, a phosphorus source, a structural director, and water to form a reaction mixture, and then converting the reaction mixture into a substantially d-spacing mixture as shown in Table 1. A crystalline aluminum phosphate composition is prepared by reacting a reaction mixture under conditions such that a crystalline aluminum phosphate composition is formed. The combination of ingredients can be accomplished in a variety of ways to make the VPI-5 compositions described. For example, an aluminum source can be mixed with water and a phosphorus source can be mixed separately with water.
The phosphorus source/water mixture is then preferably added to the aluminum source/water mixture while stirring to ensure homogeneity. The aluminum source may also be added to the phosphorus source/water mixture, or the aluminum source/water mixture may be added to the phosphorus source/water mixture. Other mixed orders are also possible. Following the preparation of a well-mixed phosphorus source/aluminum source/water precursor mixture, the precursor mixture is preferably aged sufficiently to stabilize its PH. This maturation can be carried out with or without stirring, but preferably without stirring for the time necessary for pH stabilization. Aging is preferably carried out at room temperature for 1 to 5 hours. In the preparation of the metal-substituted aluminum phosphates of the present invention, the metal source is preferably added to the aluminum source/phosphorus source/water precursor mixture after aging as described above. Also, the metal source can be added to the aluminum source/water mixture or the phosphorus source/water mixture and then the mixtures are combined. Alternatively, the metal source can be added at various stages of the synthesis. Suitable starting materials for the preparation of the aluminum phosphate or metal-substituted aluminum phosphate compositions of the invention are selected from several possible choices. Possible sources of phosphorus are e.g. elemental phosphorus,
orthophosphoric acid (H ₃ PO ₄ ), phosphoric oxides, esters of phosphoric acid, and mixtures thereof. Among these, orthophosphoric acid is preferred. Preferred aluminum sources include, for example, hydrates of aluminum such as boehmite, pseudo-boehmite,
Contains gibbsite, bayerite, and mixtures thereof. Elemental aluminum, aluminum alkoxides, aluminum oxides and mixtures thereof are also among other possible sources. The phosphorus and aluminum sources, and in the case of the silicoaluminum phosphate VPI-5, the silicon source, should be such that they can form metal oxides when incorporated into the aluminum phosphate 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 substitution examples of the invention, metal acetate dihydrates or tetrahydrates such as cobalt acetate tetrahydrate, zinc acetate dihydrate or magnesium acetate tetrahydrate are preferred, but other Metal-containing compounds are also potential sources. The metal may also be supplied as a complex ion, such as a metal oxalate, ethylenediaminetetraacetic acid complex, and the like. The next step in the synthesis is the addition of a structural director. Preferably, this is added to the aged precursor mixture. However, it is also possible to add it early in the synthesis. The structure-directing agent together with all other starting materials is called the reaction mixture.
It is preferable to age this reaction mixture for 1 to 2 hours to stabilize the pH again. Various effective structure directing agents include dipropylamine,
Diisopropylamine, tetrapyropylammonium hydroxide, tetrabutylammonium hydroxide, dipentylamine, tripentylamine, tributylamine, common alkylammonium and alkylphosphonium compounds, and mixtures thereof. Among these, dipropylamine, tetrabutylammonium hydroxide and dipentylamine are preferred, and tetrabutylammonium hydroxide is more preferred. Related molecules also serve as structure directing agents in the present invention. The proportions of reactants can vary within the ranges given. Based on the proportion of Al ₂ O ₃ molar value 1,
The molar ratio of structural director (“R”) to Al ₂ O ₃ is preferably from 0.02 to 4, more preferably from 0.2 to 2 and most preferably 1; the molar ratio of P ₂ O ₅ to Al ₂ O ₃ is Preferably 0.8 to 1.2, more preferably 0.9 to
1.1, most preferably 1; the molar ratio of water to _Al2O3 is preferably between 10 _and 100, more preferably
30-70, most preferably 35-55. When silicon or other metals (“M”) are added to make the metal-substituted aluminum phosphates of the present invention, the above ratios apply as is and further for Al ₂ O ₃
The molar ratio MOz/ ₂ is preferably from 0.001 to 0.5 mole of metal oxide per mole of Al ₂ O ₃ . Within this generally preferred range there is a difference between silicon substitutions and most other metal substitutions. That is,
The ratio to Al ₂ O ₃ is 0.2 to silicon dioxide
0.5, most preferably 0.3-0.4. On the other hand, the ratio of many other metal oxides to Al ₂ O ₃ is
It is 0.001-0.1, most preferably 0.02. In another embodiment of the invention, it is also possible to replace part of the water with a polar organic solvent. Alcohols such as hexanol or ketones or other polar solvents can also be used for this purpose. In this case, it is preferred to dissolve the structure directing agent directly in the solvent and then incorporate the agent into the oxide mixture. The minimum components of the reaction mixture, namely aluminum source, phosphorus source, structure directing agent, water and optionally additional metal sources, are combined to form a reaction mixture, and the reaction mixture is preferably heated until a nearly constant PH is obtained. Upon aging, the reaction mixture reacts under conditions such that a crystalline solid is formed that has an X-ray powder diffraction pattern that defines the VPI-5 composition. For this purpose, known heating methods are preferably used. Teflon (TEFLON) ^* (Teflon ^* is manufactured by Du Pont de Nemours.
Autoclaving in de Nemours lined cylinders is one effective and convenient means of accomplishing this. Other types of reaction vessels may be used instead. The temperature preferably ranges from 50℃ to 200℃, and from 100℃ to 150℃
℃ is more preferable. The reaction is preferably carried out under pressure, such as autogenous pressure or atmospheric pressure. Reaction times will vary in part depending on the temperature used. Insufficient heating will lead to an amorphous product, and overheating will result in the formation of an amorphous product or an undesired phase. Times of 2 to 50 hours are preferred in conjunction with temperatures of 100°C to 150°C, depending on the reactants and the composition of the reaction mixture. Following crystallization, the product is preferably subjected to conventional methods of separation and recovery. Separation from the mother liquor preferably involves filtration, but centrifugation, sedimentation and decantation, and related methods can also be used. next crystallinity
Recovery of the VPI-5 composition includes conventional washing with acid solutions such as HCl or boric acid, organic solvents such as acetone or methanol, salt solutions such as magnesium acetate or deionized water, and drying and/or heat treatment steps. These post-synthetic treatments optionally help remove structural directing agents and impart specific physical and chemical properties to the final product. The final crystalline aluminum phosphate composition is a catalyst, adsorbent ion exchanger and/or
It also exhibits molecular sieve properties and is suitable as a catalyst for reactions of various organic compounds. The following examples are provided to more fully demonstrate various embodiments of the invention. They are set forth for illustrative purposes only and are not intended or should be construed as limiting the scope of the invention in any way. Example 1 55.0 g of aluminum oxide dihydrate in 150 g of water
slurry of orthophosphoric acid (85% _H3PO4 ) _at 90%
g and 100 g of water. The resulting precursor mixture is aged at room temperature for 2 hours without stirring.
186 g of 55% tetrabutylammonium hydroxide (TBA) is added to the precursor mixture and the resulting mixture is stirred at room temperature for 2.5 hours. The composition of the reaction mixture is as follows: TBA:Al ₂ O ₃ :P ₂ O ₅ :50H ₂ O The reaction mixture is heated at 145° C. for 24 hours in a Teflon ^* lined stainless steel autoclave. Remove the product, wash with water and dry overnight at room temperature. The resulting X-ray diffraction pattern is characterized by d-spacings approximately as shown in Table 1. Example 2 Seven suspensions of aluminum oxide dihydrate are prepared as shown in Table 2. Each slurry is added to a solution of 11.38 g of orthophosphoric acid (85% H ₂ PO ₄ ) and 11.0 g of water and aged for 5 hours at room temperature without stirring. 23.54 g of 55% tetrabutylammonium hydroxide (TBA) is added to each precursor mixture with stirring to obtain the reaction mixture composition shown in Table 2.

Table: The reaction mixture is heated to 150° C. for 18 hours in a Teflon-lined stainless steel reactor.
A white solid is recovered by slurrying the contents of each reaction vessel with deionized water and allowing the solid to settle.
Dry the solid in air at room temperature overnight. The X-ray diffraction pattern of the crystalline material obtained shows a pattern characterized by d-spacings which is substantially the same as VPI-5 listed in Table 1. Example 3 About 8.9 g of aqueous orthophosphoric acid (85% strength) 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. Add the acid solution to the slurry while stirring at room temperature. The resulting precursor mixture is stirred with a magnetic bar for about 20 minutes. Prepare another solution with approximately 18.3 g of aqueous 55% tetrabutylammonium hydroxide (TBA) and approximately 10.9 g of distilled water.
Prepared by combining g. This solution is then added to the precursor mixture with stirring. Stirring is then continued for about 1.5 hours in air at room temperature. At this point the mixture has the _following molar ratio composition: 1.0TBA: _Al2O3 : _P2O5 : _52H2O Aliquots of this gel (each approximately ₂₅ % of the total volume)
into a sealed Teflon ^* -lined autoclave with an internal volume of approximately 15 ml. Heat the autoclave at approximately 150°C for approximately 44 hours. The resulting product was isolated as described in Example 1 and the first
The characteristics are as shown in the table. Example 4 About 11.50 g of orthophosphoric acid (85% concentration H ₃ PO ₄ ) is dissolved in about 9.8 g of water. Stir the solution for about 5 minutes and adjust the pH
Measure until it reaches approximately 0. The 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 before mixing it with the acid solution is about 7. The resulting precursor mixture was homogenized, first by hand and then by a magnetic stirrer, and the PH of the reaction mixture was measured over 110 minutes and is shown in Table 3: Table 3 Time PH (min) 0.72 0 1.00 15 1.20 30 1.50 45 1.60 55 1.70 70 1.70 110 Approximately 5.075 g of dipropylamine (DPrA) is added to the above premix with stirring. The resulting white reaction mixture (PH~3.8) is further homogenized for approximately 82 minutes. The result is a composition with the following molar oxide ratios: DPrA:Al ₂ O ₃ :P ₂ O ₅ :40H ₂ O This reaction mixture is then mixed with 1, 2,
Transfer to five Teflon ^* lined stainless steel autoclaves labeled 3, 4 and 5 and heat under autogenous pressure at 142° C. for the times specified in Table 4. Measure the PH for each part and observe up to PH7.0. Table 4 Experimental Time 1 20 hours 2 24 hours 10 minutes 3 25 hours 10 minutes 4 25 hours 10 minutes 5 25 hours 10 minutes The contents of each autoclave were slurried separately with deionized water and stirred for several minutes. The white solid is recovered by allowing the solid to settle and discarding the supernatant. This solid is then filtered and placed in the oven.
Dry at 100°C and exhibit the characteristics according to Table 1. Example 5 Five solutions of orthophosphoric acid (85% concentration)
Prepare as shown in the table. Each solution is added dropwise to a slurry of aluminum oxide dihydrate and water. The resulting precursor mixture is heated at the temperature and time shown in Table 5. Dipropylamine in the amount shown in Table 5 is added dropwise and the resulting reaction mixture is stirred for several minutes.

[Table] Each reaction mixture was then poured into a stainless steel Teflon plate.
^* Heat in a lined autoclave at the temperature and time shown in Table 6. A white solid is recovered by slurrying the contents of each reaction vessel with deionized water and allowing the solid to settle. The solid is then dried in air overnight at room temperature. The X-ray diffraction pattern of each of the crystalline solids obtained is characterized by the d-spacings substantially as shown in Table 1.

【table】

[Table] 〓〓 indicates no data.
_The reaction composition for all experiments was DPrA: _Al2O3 : _P2
O ₅ :37H ₂ O and further exhibits the characteristics according to Table 1. Example 6 Four solutions of orthophosphoric acid (85% H ₃ PO ₄ ) and water are prepared using ingredients as shown in Table 7. Each solution is added dropwise to the slurry of aluminum oxide dihydrate and water as indicated in the table. The obtained precursor mixture is stirred and the pH is measured. Each of the reaction precursor mixtures obtained by dropwise addition of dipentylamine (DPtA) is again stirred for the indicated time.

Table: The reaction mixture is heated in a stainless steel Teflon ^* lined autoclave for a period of time as shown in Table 8. The white solids are recovered by slurrying the contents of each reaction vessel with deionized water to allow the solids to settle and then washing with acetone. The solid is dried in air at room temperature overnight and exhibits the characteristics according to Table 1.

【table】

[Table] * represents the precursor mixture ** represents the 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 aqueous 95% dipentylamine is then added to the homogeneous precursor mixture with stirring, followed by about 10.9 g of distilled water. Stirring of the resulting reaction mixture is continued for a further 4.5 hours at room temperature in air. The reaction mixture has the following molar composition: DPtA: _Al2O3 : _P2O5 : _40H2O Aliquots of the aged mixture (approximately 25% _of the total volume each ₎ are transferred to a Teflon ^* -lined autoclave and subjected to autogenous pressure. Heat to 150°C. The solid product was then separated from the mother liquor by filtration and recovered by slurrying the contents in each autoclave in approximately 100 ml of distilled water, stirring for several minutes, allowing the solids to settle by weight, and then discarding the supernatant. do. The solids are then filtered and approx.
Dry in air at 100°C for 30 minutes. Example 8 Using the same method as in the previous example, a solution of orthophosphoric acid is prepared and then added to a slurry of aluminum oxide dihydrate. The amounts of starting materials are shown in Table 9. Stirring and heating at ambient temperature are performed as shown in Table 10, with the range of reaction compositions shown in Table 11. Aliquot the reaction mixture to approximately 15 ml.
Place in a Teflon ^* lined autoclave with internal volume sealed. Heat the autoclave to the specified temperature and time. The resulting product is a white solid that is recovered by slurrying the contents of the reaction vessel with deionized water and allowing the solid to settle. This is dried in air at room temperature overnight.

【table】

[Table] 〓〓 indicates no data. Calculating from the above information, it can be seen that there is a molar ratio range of the reactant composition as shown in Table 11 below, and the said composition further exhibits the characteristics shown in Table 1. Table 11 Experimental composition 1 TBA: Al ₂ O ₃ : P ₂ O ₅ 48H ₂ O 2 TBA: Al ₂ O ₃ : P ₂ O ₅ 20H ₂ O 3 TBA: Al ₂ O ₃ : P ₂ O ₅ 30H ₂ O 4 TBA: Al ₂ O ₃ : P ₂ O ₅ 40H ₂ O 5 TBA: Al ₂ O ₃ : P ₂ O ₅ 50H ₂ O Example 9 8.9 g of orthophosphoric acid (85% H ₃ PO ₄ ) and 6.0 g of water Add the solution prepared in g to a slurry of 5.3 g of aluminum oxide dihydrate in 6.0 g of water. Homogenize this precursor mixture for several minutes. Aqueous 55% by weight tetrabutylammonium hydroxide (TBA) 18.3g
A second solution is prepared by adding 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: 1.0 TBA: Al ₂ O ₃ : P ₂ O ₅ : 0.4 SiO ₂ : 50 H ₂ O A portion of the mixture is transferred to a 15 ml Teflon ^* lined stainless steel autoclave containing approximately 60 Fill to capacity %. Heat the autoclave to 150 °C under self-generated pressure for at least 44 hours.
The product was recovered as described in Example 8 and characterized according to Table 1. Example 10 A solution is made with 8.9 g of 85% orthophosphoric acid and 6 g of water.
This is aluminum oxide dihydrate in 6 g of water.
Add 5.3g to the slurry. Homogenize this for a few minutes and add 2.5 g of 40% low sodium colloidal silica. The resulting gel is aged for 1 hour at room temperature without stirring. A solution of 10.9 g of water and 18.3 g of 55% tetrabutylammonium hydroxide is then added. _The reactant composition is as follows: TBA: _Al2O3 : _P2O5 :0.4SiO2 _{: 50H2O} The gel was incubated for 41 hours as described in the _previous example.
Heat at 150℃. A white solid is recovered by slurrying the contents of the reactor with deionized water and allowing the solid to settle. The solid is dried in air at room temperature overnight and exhibits the characteristics according to Table 1. Example 11 11.5 g orthophosphoric acid (85% H ₃ PO ₄ ) and water
Stir the solution prepared with 9.8 g for 20 minutes. A slurry consisting of 6.8 g of aluminum oxide dihydrate and 20 g of water is stirred for 15 minutes. The phosphoric acid solution is then added to the aluminum-containing mixture with stirring. Approximately 0.93 g of humid silica is then added. The silicoaluminum phosphate precursor mixture is homogenized for 2 hours, during which time the PH of the mixture increases from 0.9 to 1.6 and stabilizes at 1.6. Approximately 6.87 ml of dipropylamine (DPrA) is then added to the mixture with constant stirring. The gel is then homogenized for 4 hours or more. This gel has an oxide composition: DPrA: _Al2O3 : _{P2O5 : 0.3SiO2} : _40H2O A portion of the mixture was transferred to a Teflon ^* -lined autoclave and kept under autogenous pressure for _at least 24 hours.
Heat to 142℃. The white solid product is recovered by slurrying the contents of each autoclave with water, stirring for several minutes, allowing the solids to settle, and discarding the supernatant. The solids were then filtered and dried in an oven at 100°C.
The characteristics are shown in Table 1. Example 12 Approximately 11.5 g of orthophosphoric acid (85% H ₃ PO ₄ ) and 9.7 g of water
Dissolve in g and stir. 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 was aged while the 13th
Stir at room temperature for the period indicated in the table. At this point, the amount of metal compound shown in the table is added with stirring at room temperature. _Al2 both before and after addition of all compounds
The total stirring time defined for O ₃ /P ₂ O ₅ mixture stirring is shown in the table. Separate reaction mixtures are prepared using magnesium, cobalt, and zinc in varying proportions. The percentage of water is also indicated. Use water in all cases. This is also shown in the table. An amount of dipropylamine (DPrA) is then added dropwise. The reaction mixture is heated in a stainless steel Teflon ^* lined autoclave for the times indicated in the table. The resulting solids are recovered by slurrying the contents of the reactor with deionized water and allowing the solids to settle. Dry the solid in air at room temperature overnight;
The characteristics are shown in Table 1. Specific reactants and method variations are shown in Table 12.

EXAMPLE 13 To better understand the properties of the VPI-5 of the present invention, it was preheated to at least about 350° C. for at least 1 hour and exhibiting the unique X-ray diffraction pattern of Table 1 above. Adsorption experiments were performed on samples of VPI-5 cooled to room temperature under reduced pressure. The sample is then exposed to a given adsorbate atmosphere until equilibrium absorption is obtained. Equilibrium was defined as a constant weight of sample and adsorbate for at least about 2 hours. The results of these experiments are shown in Table 13. This includes adsorption data for water, oxygen, nitrogen, cyclohexane, neopentane and triisopropylbenzene. This table shows adsorption data for VPI-5 prepared with two different structural directing agents, dipropylamine and tetrabutylammonium hydroxide. Also, three other reported substances, namely Zeolite Y (U.S. Patent No.
3216789) and molecular sieves
Adsorption data for AlPO ₄ -5 and AlPO ₄ -8 (as described in US Pat. No. 3,414,602) are also shown. From this table, molecules with dynamic diameters ranging from about 3 angstroms to about 14 angstroms
It can be seen that it is possible to enter the internal crystal-independent micropores of VPI-5.

【table】