JPH03505720A - Crystalline aluminum phosphate composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Crystalline Aluminum Phosphate Composition The present invention provides a crystalline aluminum phosphate composition. with respect to large pore crystalline aluminum phosphate compositions and their Regarding the manufacturing method.

Molecular sieves have been well known in the art for many years. Generally these are two There are two types: a zeolite type made of crystalline aluminosilicate molecular sieves; The crystalline aluminosilicate composition is not other molecular sieves.

Naturally occurring and synthetic analogs of zeolites include compositions of more than 100. zeola By definition, it is a tectosilicate, which means that its backbone consists of oxygen atoms and vertices. It is a three-dimensional structure consisting of Sin, -' and AIO, -5 tetrahedra that share means.

Zeolites have a porous structure with openings of uniform diameter; ion exchange capacity; reversibly adsorbs and desorbs molecules into the interstices present in the crystal through the openings and openings. It is characterized as the ability to These hole openings are To4 tetrahedrons (where T is Ke Represents either an ion or an aluminum atom. ) is defined by the combination of

Zeolites are generally synthesized from reactants in a closed system using a hydrothermal process. . Empirical data on synthetic compositions and conditions leading to zeolite formation given Numerous inventories of are available in the literature. Practices produce various zeolites The same starting materials, depending on the raw materials, mixing methods and crystallization means used, It shows that it can be obtained from

Other crystalline molecular sieves that are not zeolites are also good (known; silica polymorphism It is described in National Patent No. 4.061,712, which shows molecular sieve properties but is not explicitly described. Lacks ion exchange ability. , crystals with molecular sieve properties representing a new class of adsorbents Aluminum phosphates are described in U.S. Pat. No. 4,310,440. Ru. Some of the properties of these aluminum phosphates are similar to those of zeolite-based molecular sieves. therefore they are useful as catalytic bases or catalysts in various chemical reactions. It is. U.S. Patent No. 4,440,871 and European Patent Application No. 0146 No. 389, similar to zeolite and/or aluminum bosphate molecular sieves. Crystalline silicoaluminum phosph with molecular sieve, ion exchange and catalytic properties of The rate is listed.

Molecular sieve, ion exchange and catalytic properties similar to those of zeolites also It has also been found in rosilicate. This replaces silicon or aluminum Also using elements such as beryllium, boron, gallium, iron, titanium and phosphorous It is. These are E, Moretti et al. Zeolite synthesis in the presence of organic components (Zeolite 5ynthes) isin the Presence of Organic Compone nts)"Kimika e Industry a), 67 (1985) 21-34.

However, all of the crystalline substances mentioned above have an independent range of about 2.1 to about 7.4 people. It is known to have pores. The largest pore is defined by a ring of 12 TO4 tetrahedra. It seems that it is.

To date, there are no reports on the synthesis of non-zeolitic molecular sieve compositions with larger pores. Although there are ports, these reports have not been substantiated. For example, the US Aluminum referred to as AlPO4-8 in patent no. 4.310.440 A phosphate composition (see Example 62-A of that patent) is described, which This is perfluorotributylamine, PFTBA [(C4F9)sN)] It has been reported that it adsorbs a considerable amount of PFTBA has a kinetic diameter of approximately 1 OA. It is known to do. R, M, Barrer (R, M, Barrer), Zeolites and Clay Minerals (Zeolites and CIay) Minerals) (1978) 7. British Patent No. 1.394.163 Similar claims have been made regarding zeolites referred to as AG-4. Ru. However, none of these documents shows that PFTBA molecules are microscopic by themselves. The pores may be hair-like pores between crystalline particles or may be either crystalline or amorphous. does not provide enough data to conclusively determine whether adsorption occurs in pure substances .

Other materials reported to have large pores are described in U.S. Pat. No. 3,567.372. Z-21 and described in U.S. Pat. No. 3,414.602 Zeolite N is similar to -21. More recently, Russian engineers have Claims are made for large pore zeolites based on folding data (“Neoorganischeski Materialy (Neorganicheskie Material) Izuvestiya Academy A kademii Nauk 5SSR) 17, 6 (June 1981) 101 See 8-1021.

Therefore, in this case, crystalline aluminum having a three-dimensional microporous crystalline skeleton structure is phosphate composition, expressed by the molar ratio of its oxides The composition is A1□Ox: 1.0±0.2pzo.

and is further measured using CuK-α radiation as substantially shown in Table 1. and an X-ray powder diffraction pattern characterized by a d-spacing at 2θ of less than about 40' What is defined as having is provided.

The present invention further provides structure-directing agents. crystalline aluminum phosphate with a three-dimensional microporous crystalline skeleton structure containing The chemical composition expressed in molar ratio is XR:ALzO+: 1.0+0.2 p2o.

, where AlzOi and PzOs form an oxide lattice; R is the structural designation and x>o; the structure is further substantially as shown in Table 1 Due to the d-spacing at 2θ of less than about 40' when measured using CuK-α radiation as Defined as having a characteristic X-ray powder diffraction pattern.

The present invention also provides methods for preparing these crystalline aluminum phosphate compositions. and the method provides a method in which the chemical composition expressed in molar ratio is Ah (h: 1.0 + 0.2 pzos: 10-100 H2O and further 0.02 to 4.0 moles of structure director for each mole of Altos. From the precursor mixture, combine the aluminum source, phosphorus source and water to form the precursor mixture. the precursor mixture and the structural director to form a reaction mixture, e.g. Less than about 40" when measured using CuK-α radiation substantially as shown in Table 1. Crystalline aluminum phosphate composition characterized by a full 2θ d-spacing consists of reacting a reaction mixture under conditions such that a product is formed .

The present invention further provides a crystalline metal having a three-dimensional microporous crystal skeleton structure containing a structure directing agent. A substituted aluminum phosphate composition, the chemical composition expressed in molar ratios The composition is XR: Al2O2: 1.0±0.2 PzOs: 0.01-0.5 MOz8: 10-100Hz.

And its NA1z03. PzOs and MOz/z form an oxide lattice; R is a structural indicator; X〉0 and -M is a metal; Z is the oxidation state of M; ri; MOz/z is at least one metal oxide; the chemical composition is also one the structure is further substantially as shown in Table 1. - characterized by a d-spacing at 2θ of less than about 40° when measured using alpha radiation; is defined as having a Xi powder diffraction pattern that .

Finally, the present invention prepares these crystalline metal-substituted aluminum phosphate compositions. The present invention provides a method for producing a chemical composition in which the chemical composition expressed in molar ratio is AI, O:l: 1.0±0.5 hog: 0.001 0.5 M Oz/z: 10 1.00820 , where M is the metal; Z is the oxidation state of M; MOz/z is the at least one metal oxide; the chemical composition further includes one or more charge-correcting species and Al from a precursor composition comprising 0.02 to 4 moles of structure director for each mole of z(h) , an aluminum source, a phosphorus source, a metal oxide source and water. forming a precursor mixture and combining the precursor mixture and a structure-directing agent to form a reaction mixture; and when measured using CuK-α radiation substantially as shown in Table 1 Crystalline metal-substituted aluminum characterized by a d-spacing of approximately 40° ungrooved at 20 or reacting the reaction mixture under conditions such that a phosphate composition is formed. It is made up of

Figure 1 shows a comparison with the aluminum phosphate of the present invention designated as “VPI-5”. Shows the argon adsorption isotherm for zeolite X (Na) used for the purpose of . Zeolite X(Na) is described in US Patent No. 2.882.244.

FIG. 2 shows an embodiment of the aluminum phosphate of the present invention represented by VPI-5. The composition is a synthetic crystalline aluminum phosphate material, hereinafter referred to as "VPI-5". ”. This is an intramolecular combination of large molecules such as triisopropylbenzene. It is a substance that reversibly adsorbs and desorbs from crystal pores. These materials are three-dimensional microporous Consists of a crystalline skeleton structure.

These aluminum phosphate materials can be characterized in a number of ways. in general , the basic chemical composition of the molecular sieve expressed in molar ratio is: Ah02: 1.0±0.2P20S, and these compositions are given in Table 1. defined by an X-ray powder diffraction pattern with a d-spacing substantially such that It has a crystal structure. As used herein, the term “substantially” refers to The given d-spacing is within the experimental error tolerance and therefore the equipment and technique This means taking into account the differences attributable to changes in In the table VPI- between about 3° 2θ and about 40° 2θ when measured using CuK-α radiation 5 shows characteristic d-spacings of 5. “Characteristic” and “distinctive” as used here mean: These d-spacings are associated with the largest peaks equal to or greater than about 10 It represents all peaks with intensity. These peaks are very strong It has a strength listed as “Vs” for hard or “m” for medium. is shown as Lower intensity peaks are described as having weak (W) intensity. and is therefore excluded from this definition. d interval is VPI-5 samples It remains almost the same even after heating to at least about 600°C. This heating is carried out, for example, in air or in an air/steam mixture under reduced pressure. Experiment The X-ray diffraction pattern was obtained in an automatic powder diffractometer using CuK-α radiation.

Table 1 X-ray powder diffraction data for synthesized VPI-5 Another property of the Based on these compositions, XR:Al2 (h: 1.O+0.2 pzos, where R is used for the synthesis of large pore materials) is the structural directing agent used, where X is A1□0. is the molar ratio value of R to X >.

It is. Since the structural directing agent is part of the preparation method as discussed below, the composition Its amount in is somewhat dependent on whether it undergoes partial desorption or decomposition.

In FIG. 1, VPI-5 aluminum phosphate of the present invention and U.S. Patent No. 2. The argon adsorption isotherm of zeolite X (Na) described in No. 882.244 is shown. vinegar. These results are consistent with the Omnisorb 360 device (at liquid argon temperature). 1 Omni Soap is Omicron Chikunoroshii Corporation 0m1cron It is a registered trademark of Technology Corporation. ) is measured in Ta. Figure 2 shows the relationship between VPI-5 and the zeolite of U.S. Patent No. 2,882,244. Indicates the effective pore diameter. Adsorption isotherms and pore size distributions were determined by Horva-Kawazoe Vath-Kawazoe) analytical method (Shi-Horvath et al. G, Horvathet 　al,,　　　Method for the Calculation of Effect Bore Size Distribution View John Inmolecular Sieve Carbon Metho d for the calculation of Effective Po re 5ize Distribution in Mo1ecular 5i eveCarbon', J, Chem, Eng, of Japan 16. (5) 470-475 (1983)). Zeolite X (N a) Faujasite structure with pore openings defined by 12-membered ring tetrahedra is a typical example, and its allowable diameter is approximately 0.8 rim. This diameter is shown in Figure 2. in good agreement with the values given. VPI-5 is substantially larger than Zeolite X(Na) It was proven that it has pores.

Therefore, from the above experiments, it can be seen that the VPI-5 composition has some of its pore spacings It has a pore system that is large enough to allow the entry and exit of sopropylbenzene molecules. It is inferred that it exhibits a crystal structure of Used for molecules with smaller pore spacing It is possible.

Metal-substituted aluminum phosphates were also characterized through X-ray diffraction. view The observed powder pattern was similar to that obtained with unsubstituted VPI-5 as shown in Table 1. Showing the same featured d-spacing. These metal-substituted aluminum phosphates are P A similar molar ratio of A1□03 to ZOs is shown. Generally these compositions are: Defined by molar ratio: Al2O3: 1.0±0.2 PzOs: 0.01 0.5 MOZ/ 2,: 10-100H,0 In this formula M is the metal, Z is the acid value state of M, and MOz/2 is At least one metal oxide. For example, silicoaluminum phosphate Formula % Formula % indicating the molar ratio of the composition The structural director is unsubstituted aluminum for metal-substituted aluminum phosphate compositions. present in the same proportions as to the aluminum phosphate composition, and The same choices for the carbon source as well as the structural directing agent would be appropriate. Similarly, the structural director is , whether desorption or decomposition has occurred, the final silicoaluminum Sphate νl’! -5 remains in the composition, but also does not remain. Further chemistry class The composition is charge-corrected for the metal-substituted alumina 1 phosphate species, thereby reducing the charge. Contains one or more counterbalances. These charge correction species are e.g. Select from various cations or anions such as chloride, hydroxide, chloride, etc. can be selected and known to those skilled in the art.

Other elements from sources that can form oxides may also be present in X-ray powder diffraction patterns or A basic VPI-5 aluminum phosphor that does not significantly affect the general oxide lattice structure. It is also possible to substitute a phase crystal skeleton structure. These include titanium, tin, etc. , Kobal), zinc, magnesium, zirconium and mixtures thereof. Contains substituted metals.

The invention also comprises a method for preparing the VPI-5 compositions described herein. In general, the reaction The specific molar ratios of the components are important in obtaining the final crystalline solid according to the above characteristic data. It is essential. In summary, the crystalline aluminum phosphate of the present invention contains aluminum combining a source, a phosphorus source, a structural director, and water to form a reaction mixture; The reaction mixture is then converted to a crystallinity characterized by substantially d-spacing as shown in Table 1. React the reaction mixture under conditions such that aluminum phosphate W acid is formed. It is prepared by

The ingredients may be combined in various ways to produce the VPI-5m acid described. I can. For example, an aluminum source is mixed with water, and a phosphorus source is mixed with water. can also be mixed separately with water. The phosphorus source/water mixture is then preferably Add Luminilla l to the source/water mixture and stir while ensuring homogeneity. Also, Add the aluminum source to the phosphorus source/water mixture or The source/water mixture may be added to the phosphorus source/water mixture. Other mixed orders can also be used. Available for use.

Following the preparation of a well-mixed phosphorus source/aluminum source/water precursor mixture Preferably, the precursor mixture is sufficiently aged to stabilize its pH. this Ripening can be carried out with or without stirring, but l) H Preferably, stirring is not carried out for the required period of time. Aging at room temperature for 1-5 hours It is preferable to do so.

In the preparation of the metal-substituted aluminum phosphates of the present invention, the metal source is Add to the aluminum source/phosphorus source/water precursor mixture after aging as described above. is preferred. Alternatively, replace the metal source with an aluminum source/water mixture or a phosphorus source. It can also be added to the source/water mixture and the mixture then combined.

Alternatively, the metal source can be added at various stages of the synthesis.

Aluminum phosphate or metal substituted aluminum phosphate of the present invention-1. Suitable starting materials for the preparation of the composition are selected from several possible options. Rin's capacity Possible sources include, for example, elemental phosphorus, orthophosphoric acid (H:1PO4), phosphorus oxides. , esters of phosphoric acid, and mixtures thereof. Among these, orthorin Acids are preferred. Preferred aluminum sources are e.g. aluminum hydrates. For example, bemite, pseudo-boehmite, gibbsite, bayerite, and and mixtures thereof. Aluminum element, aluminum alkoxide, aluminum Minium oxides and mixtures thereof are also among other possible sources. Rin Source and Aluminum Source and Silicoaluminum Phosphe-1-V In the case of PI-5, the silicon source is mixed into the aluminum phosphate lattice. They should be able to form metal oxides when preferred silicon Sources include humid silica, aqueous colloidal silica, and tetraethylorthosilica. silica and other reactive silicas. Other silicon-containing compounds can also be used. Ru. In other metal substitution examples of the invention, metal acetate dihydrates or tetrahydrates, etc. For example cobalt acetate tetrahydrate, zinc acetate trihydrate or magnesium acetate tetrahydrate metal-containing compounds are preferred, but other metal-containing compounds are also possible sources.

Metals can also be used as complex ions, e.g. metal oxalates, ethylenediaminetetra It may also be supplied as an acetic acid complex or the like.

The next step in the synthesis is the addition of a structural director. This is a mature precursor mixture It is preferable to add it to. However, adding this early in the synthesis is also possible. 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 useful structure-directing agents include dipropylamine, diisopropylamine, and tetrapropylamine. Lopylammonium hydroxide, TeI butylammonium hydroxide, dipentylamine, tripentylamine, tributylamine, general alkylamine ammonium and alkylphosphonium compounds, and mixtures thereof. . Among these, dipropylamine, tetrabutylammonium hydroxide and and dipentylamine are preferred, and tetrabutylammonium is more preferred. Hydroxide. Related molecules also serve as structural directing agents in the present invention .

The proportions of reactants can vary within the ranges given. A1□03 Percentage in molar value 1 The molar ratio of structural director (“R”) to Ah (h) is preferably 0 ．． 02-4, more preferably 0, 2-2, most preferably 1; The molar ratio of PzOs to PzOs is preferably 0.8 to 1.2, more preferably 0.9 to 1.2. 1,1, most preferably 1; the molar ratio of water to Alzl; h is preferably preferably 10-100, more preferably 30-70, most preferably 35-55. Ru. Silicon or other metals (“M”) can be added to the metal-substituted aluminum foils of the present invention. When making spheres, the above ratios are applied as is and further applied to Atzoi. The molar ratio of MOz/z is preferably 0.0 mole of metal oxide per mole of A1□0. 01 to 0.5 mol is preferred. Within this generally preferred range, silicon substitutes and There are differences between most other metal substitutes. In other words, the ratio to A1□03 is 2 0.2 to 0.5 relative to silicon oxide, most preferably 0.3 to 0.4. Ru. On the other hand, the ratio of many other metal oxides to AhOz is between 0.001 and 0.1. Yes, 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. be. Alcohols such as hexanol or ketones or Other polar solvents can also be used. In this case, the structural director may be dissolved directly in the solvent. Preferably, the agent is then incorporated into the oxide mixture.

Minimum components of the reaction mixture: aluminum source, phosphorus source, structure directing agent , water and optionally an additional metal source to form a reaction mixture, and This reaction mixture is preferably aged until a nearly constant pH is obtained, and the reaction mixture The VPI-5 composition is a crystalline solid having an X-ray powder diffraction pattern that defines it. react under conditions such that they are formed. In contrast, known heating methods are preferably used. used. Teflon (TEFLON) Teflon 9 is DuPont Donemour Du Cylinder lined with Pont deNen+ours (trade name) Autoclaving in a container is one effective and convenient means of achieving this.

Other types of reaction vessels may be used instead.

The temperature preferably ranges from 50°C to 200'C, and from 100'C to 150°C. °C is more preferred. The reaction is preferably carried out under pressure, e.g. under autogenous pressure or It is carried out under atmospheric pressure.

Reaction times vary in part depending on the temperature used. Insufficient heating will result in amorphous Overheating may lead to the formation of amorphous products or undesired phases. result. A time period of 2 to 50 hours is preferred in conjunction with a temperature of 100"C to 150C. and these depend 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 filtration are preferred. Cantation, recovery of the VPI-5 composition is performed using an acid solution such as I (CI or fluoride). Uric acid, organic solvents such as acetone or methanol, salt solutions such as magnetic acetate. Regular cleaning with deionized water and drying and/or heat treatment. Includes physical processing. These post-synthesis treatments can help remove structural directing agents if desired. and impart specific physical and chemical properties to the final product. The last crystalline a The aluminum phosphate composition has catalytic, adsorbent ion exchange and/or 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. child They are set forth for illustrative purposes only and may not be used in any way. It is not intended or should be construed as limiting the scope of the invention. stomach.

Example 1 A slurry of 55°Og of aluminum oxide source in 150g of water was prepared using orthophosphoric acid. Add to a solution of 90 g of acid (85%) 12PO4) and 100 g of water. before got The precursor mixture is aged at room temperature for 2 hours without stirring. 55% tetrabutyluane Add 186 g of monium hydroxide (TBA) to the precursor mixture and The mixture is stirred at room temperature for 2.5 hours. The composition of the reaction mixture is as follows: TBA: AhOs: PzOs: 50 HzO The reaction mixture was immersed in Teflon. Heated at 145°C for 24 hours in a 9-lined stainless steel autoclave do. Remove the product, wash with water and dry overnight at room temperature. Obtained X-ray diffraction The pattern is characterized by d spacing approximately as shown in Table 1.

Example 2 Seven suspensions of aluminum oxide trihydrate are prepared as shown in Table 2. Each space The slurry was dissolved in 11.38 g of orthophosphoric acid (85% n, po;) and 11.0 g of water. Add to the solution and age at room temperature for 5 hours without stirring. 55% tetrabutyla Mix each precursor while stirring 23.54 g of ammonium hydroxide (TBA) The reaction mixture composition shown in Table 2 is obtained.

6.25 TBA:PzOs:0.90 Al2O2:40 Hz06. 59 TB^: hOs: 0.95 Al2O2: 40 Ht: 06.73 　　　　TBA:hos:0.97　AlzO+:40　Hz06.94　 TBA:PzOs: 1.00 AlzOs: 40 Hz07.15 TBA:P2O5: 1.03 Al2O2:40HzO7,29TBA:P zOs: 1.05 Alz (h: 40 HzO7,63TBA:PzOs: 1 ．． 10　Al□03:40　) 120 reaction product was placed in a Teflon-lined step Heat to 150°C for 18 hours in a stainless steel reactor. Perform each reaction with deionized water. A white solid is recovered by slurrying the contents of the container and allowing the solid to settle. solid The bodies are dried overnight in the air at room temperature. The X-ray diffraction pattern of the crystalline material obtained is essentially A putter characterized by a d-spacing that is the same as VPI-5 listed in Table 1. Indicates the

Example 3 Approximately 8.9 g of aqueous orthophosphoric acid (85% concentration) is dissolved in approximately 6.0 g of distilled water. child Separately, about 5.3 g of aluminum oxide dihydrate can be mixed with about 6.0 g of distilled water. A slurry is prepared by Add acid solution to slurry while stirring at room temperature . The resulting precursor mixture is stirred with a magnetic bar for about 20 minutes.

Another solution was prepared in an aqueous 55% tetrabutylammonium hydroxide (TBA) containing approximately 1 Prepared by combining 8.3 g and 10.9 g of distilled fishing rod. Then this Add the solution to the precursor mixture while stirring. Then in air at room temperature for about 1.5 hours. Continue stirring for a while.

At this point the mixture has the following molar ratio composition: 1, OTBA:AIZ(h : p, os : 52 HzO Aliquots of this gel (approximately 25 %) into a sealed Teflon 1-lined autoclave with an internal capacity of 15 m. put in. Heat the autoclave at about 150°C for about 44 hours. the resulting generation The product was isolated as described in Example 1 and characterized as shown in Table 1.

Example 4 Dissolve approximately 11.50 g of orthophosphoric acid (85% concentration H, PO4) in 968 g of fishing rod. vinegar. Stir the solution for about 5 minutes and measure the pit to about O. Next, water 20 ．． In Og, 6.875 g of aluminum oxide dihydrate was stirred for about 5 minutes. Add the above solution to the slurry prepared above. Before mixing this with the acid solution Slurry pH is approximately 7. The resulting precursor mixture was stirred first by hand and then magnetically. Homogenized by a stirrer, the pH of the reaction mixture was measured over 110 minutes and shown in Table 3. vinegar: Table 3 1.20 30 1.70 110 Approximately 5.075 g of dipropylamine (DPrA) was added to the above premix with stirring. Add. Further homogenize the resulting white reaction mixture (pH ~3.8) for approximately 82 minutes. do. The result is a composition expressed in molar oxide ratios: DPrA: AIZO: I: PzOs: 40 HzO Then this reaction The reaction mixture was transferred to five 1-L Teflon tubes labeled 1.2, 3.4, and 5, respectively. Transfer to an inning stainless steel autoclave for the times specified in Table 4. Heat under autogenous pressure at 142°C. p) Measure l for each part. , observe pH up to 7.0.

Table 4 Emperor - Kasa - Ichiichi - Kanichi 1 20 hours 2　　　　　24 hours 1o minute 3　　　　　　25 hours 1o minutes 4 25 hours 1o minutes 5 25 hours 10 minutes Slurry the contents of each autoclave separately with deionized water and stir for several minutes. The white solid is recovered by allowing the solid to settle and discarding the supernatant. then The solid is filtered and dried in an oven at 100°C, exhibiting characteristics according to Table 1. .

Example 5 Five solutions of orthophosphoric acid (85% strength) are prepared as shown in Table 5. Each melt The liquid is added dropwise to the slurry of aluminum oxide dihydrate and water. The obtained precursor mixture The mixture is heated at the temperature and time shown in Table 5. Dipropylua in the amounts shown in Table 5 Minutes are added dropwise and the resulting reaction mixture is stirred for several minutes.

Δ1,0. 13.75 6.875 6.875 13.75 6.875H3PO-23,011,511,523,OH,5DPrA 10.15 5.075 5.075 10.15 5.07 Wednesday 59.6 29.8 29.8 59.6 29 ．． 8 Each reaction mixture was then placed in a stainless steel Teflon-lined autoclave. Heating is performed at the temperature and time shown in Table 6. Pour the contents of each reaction vessel into deionized water. A white solid is recovered by slurrying and settling the solid. Then the solid Dry in air overnight at room temperature. The X-ray diffraction pattern of each of the obtained crystalline solids is , substantially characterized by the d-spacings shown in Table 1.

-- indicates no data t''.

The reaction composition for all experiments was DPrA: A1z03: P2O5: 37H 2O and further exhibits the characteristics according to Table 1.

Example 6 Four solutions of orthophosphoric acid (85% H, PO,) and water were prepared as shown in Table 7. Prepare using minutes. Transfer each solution to a slurry of aluminum oxide dihydrate and water. Add dropwise as shown. The resulting precursor mixture is stirred and the pH is measured. Dipenci The indicated times for each of the reaction precursor mixtures obtained by dropwise addition of DPtA Stir again.

Alz(h 5.3 10.5 15.75 6.875H, Po, 8.9 17.8 23.0 11.5DPtA 7.89 15.7B 15.78 7.89Wed 1 2 36 59.6 39.8 reaction mixture in Table 8 Stainless steel Teflon lined autoclave as shown. Heat for a certain amount of time.

Slurry the contents of each reaction vessel with deionized water to allow solids to settle, then add acetic acid to Collect the white solid by washing with water.

The solid is dried in air at room temperature overnight and exhibits the characteristics according to Table 1.

1 = table pH 1,78" 1.90° 1.70'" * represents the precursor mixture vinegar **represents reaction mixture Example 7 Approximately 8.9 g of orthophosphoric acid HffPO4 is not dissolved in approximately 6.0 g of distilled water.

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

Approximately 7.89 g of aqueous 95% dibentylamine was then homogeneously mixed into the precursor with stirring. Then add 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. reaction The mixture has the following molar ratio composition: DPtA: Al2O2: has: Aliquots (approximately 25% of the total volume each) of the 40 Hz0 aged mixture were transferred to Teflon. Transfer to a lined autoclave and heat to 150°C under autogenous pressure. .

The solid product is then separated from the mother liquor by filtration and drained into each autoclave. Slurry the contents in approximately 100 g of distilled water, stir for several minutes, and let the solids settle by weight. The supernatant is then collected by discarding the supernatant. The solids are then filtered and Dry in air at 100°C for approximately 30 minutes.

Example 8 Using the same method as in the previous example, a solution of orthophosphoric acid was prepared and then an alkali oxide solution was prepared. Add to the mini dihydrate slurry. The amounts of starting materials are shown in Table 9. atmosphere Stirring and heating at temperatures as shown in Table 10 produced reactions as shown in Table 11. It has a range of compositions. Aliquot the reaction mixture into a sealed container of approximately 15-internal volume. Place in a Teflon-lined autoclave. Bring the autoclave to the specified temperature. Heat according to the degree and time. The product obtained was a white solid which was reacted with deionized water. It is recovered by slurrying the contents of the reaction vessel and allowing the solids to settle. this Dry overnight in air at room temperature.

】”L table AI□0. 5.3 1i, 15 11.15 11.15 5.72H, PO48,917,817,817,88,9TBA 18.3 36.6 36.6 36.6 18 ．． 3 water 32.9 11.6 25.65 39.6 9 35 Heating time 5 hours 5 days 5 days 5 days 41 hours 44 hours- 1 represents no data Calculating from the above information, the molar ratio range of the reactant composition is as shown in Table 11 below. It can be seen that the said composition further exhibits the characteristics according to Table 1.

Table 11 JLJi u I TBA: Ah (h: p, o,: 48 H2O2TB A: A12os: PzOs: 20Hz03 TBA: 81□03: P2O5: 30 HzO4TBA ;　AlzOz　:　p,o,　: 40　HzO5TBA　:　Al□(h ” has: 50 H20 Example 9 A solution prepared with 8.9 g of orthophosphoric acid (85% thPo4) and 6.0 g of water was Water 6. Add to a slurry of 5.3 g of aluminum oxide dihydrate in Og. before this Homogenize the precursor mixture for several minutes. Aqueous 55% by weight tetrabutylammonium hydride Roxid (TBA) 18.3g and humid silica 0.928g water 10.9g Prepare a second solution by adding to g. While mixing this second solution and homogenize the resulting reaction mixture for 90 minutes. The reaction mixture is has the following: ], QTBA: 81□0+: PzOs: 0.4 SiO□: A portion of the 50H20 mixture was poured into a Teflon 9-lined stainless steel tube with an internal capacity of 15 d. When transferred to a molded autoclave, it was filled to approximately 60% by volume. autoclave to 150'C under autogenerated pressure for over 44 hours. Record the product in the example date. It was collected as shown in Table 1 and the characteristics are shown in Table 1.

Example 10 Make a solution with 8.9 g of 85% orthophosphoric acid and 6 g of water. Add this to the oxidized acid in 6 g of water. Add to the slurry of 5.3 g of luminium dihydrate. Homogenize this for a few minutes until 40% Add 2.5 g of low sodium colloidal silica. Do not stir the resulting gel. Aginate for 1 hour at room temperature. Next, 10.9 g of water and 55% tetrabutylammonium A solution of 18.3 g of hydrochloride is added. The reactant composition is as follows: TBA: AhO* Two has: 0.4 SiO□ :50 H2° gel was incubated at 150°C for 41 hours as described in the previous example. Heat it up. Slurrying the contents of the reactor with deionized water and allowing solids to settle out. Collect a white solid. The solid was dried overnight in air at room temperature and given the characteristics according to Table 1. show signs.

Example 11 Prepared with 11.5 g of orthophosphoric acid (85% HxPOa) and 9.8 g of water. Stir the solution for 20 minutes. 6.8g of aluminum oxide trihydrate and 20g of water Stir the slurry for 15 minutes.

The phosphoric acid solution is then added to the aluminum-containing mixture with stirring. Huyumd Approximately 0.93 g of silica is then added. Contains silicoaluminum phosphate precursor The mixture was homogenized for 2 hours, during which time the pH of the mixture increased from 0.9 to 1.6 and 1. ．． Stable at 6.

Next, about 6.87 d of dipropylamine (DPrA) was added to the mixture with constant stirring. Add to. The gel is then homogenized for 4 hours or more.

This gel has an oxide composition: DPrA: AlzOi: P2O3: 0.35i (h: 40 HzO Transfer a portion of the mixture to a Teflon 9-lined autoclave for at least 24 hours. Heat to 142°C under autogenous pressure.

Slurry the contents of each autoclave with water and stir for several minutes to allow solids to settle. , collect the white solid product by discarding the supernatant. The solids are then filtered and It is dried in an oven at 100° C. and exhibits the characteristics according to Table 1.

Example 12 Dissolve about 11.5 g of orthophosphoric acid (85% H, PO4) in 9.7 g of water and stir do. Add this solution to a slurry of 6.7 g of aluminum oxide dihydrate and 20 g of water. Add dropwise. The resulting precursor mixture was aged while stirring at room temperature for the period shown in Table 13. Stir. At this point, the amount of metal compound shown in the same table is added with stirring at room temperature. all Stirring the AlzO3/F’zOs mixture both before and after compound addition The total stirring time defined is shown in the table. Separate reaction mixture, magnesium, cobal and zinc in varying proportions. The percentage of water is also indicated. All Use water if necessary. This is also shown in the table. Dipropylamine (DPr A quantity of A) is then added dropwise. Reaction mixture for the indicated time stainless steel Heat in a Teflon-lined autoclave. The obtained solid is transferred to the reactor. The contents are slurried with deionized water and the solids are recovered by settling.

The solids were dried overnight in air at room temperature and are characterized in Table 1.

Specific reactants and method variations are shown in Table 12.

Table 12 Amount (g) 2L 25 25 0.25 0.21 0.22 When heated Duration 5 hours 3 hours 3 hours 24+ 24+ 24+ hours Hours time Temperature 150°C 150°C 150°C 142°C 142°C 142°C Example 1 3 In order to better understand the properties of the VPI-5 of the present invention, the unique at least about 350°C for at least 1 hour while exhibiting a line diffraction pattern. In a sample of VPI-5 preheated to An adsorption experiment was conducted. Then, until equilibrium absorption is obtained into the atmosphere of the given adsorbate, Expose the sample. Equilibration involves keeping the sample and adsorbate together for at least about 2 hours. defined as a constant combined weight. The results of these experiments are shown in Table 13. child This includes water, oxygen, nitrogen, cyclohexane, neopentane and triisopropyl. Contains adsorption data for benzene.

This table includes two different structural directing agents, dipropylamine and tetrabutyl Adsorption data for VPI-5 prepared using ammonium hydroxide are shown. Additionally, three other reported substances, namely zeolite I-Y (U.S. 3.216.789) and molecular sieves AIPO,-5 and A for lPO4-8 (as described in U.S. Pat. No. 3,414,602). Adsorption data is also shown. From this table, approximately 3 angstroms to approximately 14 angstroms Molecules with dynamic diameters in the lohm range enter VPI-5 internal crystal-free micropores It turns out that you can do it.

6 Target of correction Translation of the description and claims 8 List of attached documents Translation of the description and claims, one copy each, written amendment July j, 1999 Yoshi, Commissioner of the Patent Office 1) Takeshi Moon 1.Display of the incident PCT/US88102910 2. Name of the invention Crystalline aluminum phosphate composition ~ 3, corrector Relationship to the case Patent applicant Name: The Dow Chemical Company 4, Agent Address: Seikou Toranomon Building, 8-10 Toranomon-chome, Minato-ku, Tokyo 105 Phone: 504 -07215, subject of correction The scope of the claims 6. Contents of amendment The scope of claims is amended as shown in the attached sheet.

7. List of attached documents Scope of claims　　　　　　　　　　　　1 copy of claim 1. It has a three-dimensional microporous crystalline structure, and its chemical composition expressed by the molar ratio of oxides is Δ1□0. : 1.0±0.2 P2O.

Furthermore, as shown in Table 1, the angle is less than about 40° when measured using CuK-α radiation. having an X-ray powder diffraction pattern characterized by the d-spacing of the grooves at 20 A crystalline aluminum phosphate composition defined as .

2. (1) Mix aluminum source, phosphorus source and water to form precursor mixture Completion; (2) mixing the precursor mixture and the structural directing agent to form a reaction mixture; (3) The reaction mixture is characterized by a crystalline solid d-spacing as shown in Table 1. The sample is heated under conditions such that it has an X-ray diffraction pattern that reflects the

The chemical composition of the precursor mixture, expressed as the molar ratio of oxides, is ＾1□o, : i, o±0.2 P2O5: 10-100 H2O It has a dimensional microporous crystalline framework structure and furthermore, for each mole of Δ1203, 0.0. A method of preparing a crystalline aluminum phosphate composition comprising 0.2 to 4.0 moles.

Koku Junjun Shunsuke Prison

Claims (1)

[Claims] 1. It has a three-dimensional microporous crystal skeleton structure, and the chemical composition expressed as the molar ratio of oxides is Al2O3: 1.0±0.2P205 Furthermore, as shown in Table 1, it is less than about 40° when measured using Cuk-α radiation. having an X-ray powder diffraction pattern characterized by a d-spacing at full 2θ. Crystalline aluminum phosphate composition defined. 2. The dynamic diameter ranges from about 3 angstroms to about 14 angstroms. A claim having an internal crystalline isolated micropore capable of containing a molecule having 1. The composition according to 1. 3. 3. A composition according to claim 2, wherein the molecule is triisopropylbenzene. 4. As shown in Figure 1, the argon adsorption isotherm of zeolite X (Na) was compared. The composition of claim 1 exhibiting an argon adsorption isotherm. 5. A composition according to claim 1, wherein Al2O3 and P205 form an oxide lattice. 6. The chemical composition expressed by the molar ratio of oxides is XR:Al2O3:1.0±0.2 P205, and in that case Al2O3 and P205 form an oxide lattice; R represents a structural director; and X>0 The composition according to claim 1, further comprising a structure-directing agent. 7. If the structural directing agent is dipropylamine, diisopropylamine, or tetrabutylamine, ammonium hydroxide, tetrapropylammonium hydroxide, dipentylic acid 7. The compound according to claim 6, wherein the Composition. 8. The structure directing agent may be present in an amount of 0.02 to 4 moles for each mole of Al2O3. The composition according to claim 6. 9. Claim 6, wherein the structure directing agent is in an amount of 1 mole for each mole of Al2O3. Composition. 10. 17. A composition according to claim 16, wherein the structure-directing agent is capable of being eliminated. 11. In addition, silicon, magnesium, titanium, cobalt, tin or zirconia Claim 1 or Claim 1 containing 0.001 to 0.5 mol of at least one metal oxide of is the composition described in 6. 12. Claim 1, wherein Al2O3, P205 and the metal oxide form an oxide lattice. 1. The composition according to 1. 13. The X-ray powder diffraction pattern of the composition after heating to at least 600°C shows that substantially When measured using Cuk-α radiation, which is shown in Table 1, it is less than about 40°. 7. The method according to claim 1 or 6, characterized by a d-spacing at 2θ of Composition. 14. Silicon oxide includes fumed silica, aqueous colloidal silica, and tetraethylol. 25. The composition according to claim 24, which is a tosilicate or a mixture thereof. 15. (1) Mixing an aluminum source, a phosphorus source, and water to form a precursor mixture. ; (2) mixing the precursor mixture and the structural directing agent to form a reaction mixture; (3) The reaction mixture is characterized by the d-spacing of the crystalline solid as shown in Table 1. The sample is heated under conditions such that it has an X-ray diffraction pattern that reflects the The chemical composition of the precursor mixture, expressed as the molar ratio of oxides, is Al2O3: 1.0±0.2P205: 10-100H20 three-dimensional microporous It has a crystalline skeleton structure and further contains 0.02-4. A method of preparing a crystalline aluminum phosphate composition containing 0 moles. 16. Claim 15, wherein the molar ratio of P205 to Al2O3 is 0.9 to 1.1. The method described in. 17. The method according to claim 15, wherein the molar ratio of water to Al2O3 is 20 to 70. Law. 18. Aluminum sources include elemental aluminum, aluminum hydrates, and aluminum oxides. Claim 15 which is aluminum, aluminum alkoxide or a mixture thereof. The method described in. 19. The phosphorus source is orthophosphoric acid, elemental phosphorus, phosphorus oxide, esters of phosphoric acid or The method according to claim 15, wherein is a mixture thereof. 20. Structural directing agents include dipropylamine, diisopropylamine, and tetrabutylamine. ammonium hydroxide, tetrapropylammonium hydroxide, dipentylic acid according to claim 15, which is triamine, tribentylamine or tributylamine the method of. 21. The composition has a dynamic range of 3 angstroms to 14 angstroms. Has an internal crystalline free-standing micropore that can accommodate molecules with a diameter 16. The method according to claim 15. 22. 16. The method of claim 15, wherein the molecule is triisopropylbenzene. 23. Compare with the argon adsorption isotherm of zeolite X (Na) as shown in Figure 1. 16. The method of claim 15, which exhibits an argon adsorption isotherm. 24. 16. A method according to claim 15, wherein the heating is carried out at a temperature of 50<0>C to 200<0>C. 25. 16. The method of claim 15, wherein heating is conducted for 1 hour to about 10 days. 26. Mix the aluminum source and a portion of the water separately, and add the phosphorus and a second portion of the water. from mixing separately and then combining the two mixtures to form the precursor mixture. 16. The method according to claim 15. 27. Aging the precursor mixture for 1 to 5 hours to reach a substantially constant pH. 16. The method according to claim 15. 28. Silicon, magnesium, cobalt, titanium, tin, zinc, zirconium or or a precursor mixture obtained by adding a metal source of these mixtures to the precursor mixture. The chemical composition expressed in molar ratio is 0.001 to 3 moles in total of metal oxides. 16. The method according to claim 15. 29. The metal source is a silicon source and the precursor mixture is 0.1 to 1 silicon dioxide. 29. The method of claim 28, comprising molar. 30. Silicon sources include fumed silica, aqueous colloidal silica, and tetraethyl silica. 30. The method according to claim 29, wherein the silicates are silicates or mixtures thereof. 31. Crystalline solids, further washed with acid solutions, salt solutions, organic solvents or deionized water 16. The method according to claim 15, further comprising: drying; and thermal treatment.