JPH0471003B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION This invention relates generally to crystalline aluminophosphate compositions, and more particularly to novel crystalline aluminophosphates of the molecular sieve type and methods of making the same. Background of the Invention It has an open skeletal structure in which tetrahedral units of AlO ₂ and PO ₂ are bonded by sharing corner oxygen atoms, and is characterized by having uniform pore sizes. Microporous crystalline aluminophosphates have been reported in many publications, especially in ST.
No. 4,310,440 to Wilson et al., published July 7, 1980. Wilson et al.'s aluminophosphates constitute a general class of non-zeolitic molecular sieve materials that are capable of complete and reversible dehydration in either anhydrous or hydrated states while retaining the same basic skeletal morphology. ing. Term "basic skeletal morphology"
Or as "basic framework" is used in the above US patents and herein, it means the spatial arrangement of the principal Al-O and P-O bonds. Also,
Other microporous aluminophosphates which undergo reversible or irreversible structural rearrangement upon partial or complete dehydration, such as the minerals varisiaite and metavarisiaite and F. D'yvoire.
Certain synthetic metastable aluminophosphates are known, reported by [Bull. Soc. Chim. France. 1762 (1961)]. A different type of synthetic crystal composition, in addition to AlO ₂ and PO ₂ tetrahedra, manganese,
Compositions containing skeletal tetrahedral metal oxides of magnesium, cobalt and/or zinc filed for U.S. patent
No. 514334 (filed on July 15, 1983). Summary of the Invention The present invention consists of a novel microporous crystalline aluminophosphate (hereinafter referred to as AlPO ₄ -39) and a method for producing the same. AlPO ₄ -39 has a basic skeletal structure whose chemical composition expressed by the molar ratio of oxides is Al ₂ O ₃ :1.0±0.2P ₂ O ₅ and has at least the d-spacing shown in the table below. An X-ray powder diffraction pattern including the following is shown. AlPO ₃ -39 is produced by hydrothermal crystallization from a reaction mixture containing, in addition to water, a reactive source of aluminum and phosphorus and an organic templating agent, preferably an alkylamine, most preferably di-n-propylamine. can do. DETAILED DESCRIPTION OF THE INVENTION The novel microporous aluminophosphates of the present invention are capable of absorbing heat from a reaction mixture containing a reactive source of phosphorus and aluminum and an organic templating agent, preferably di-n-propylamine (Pr ₂ NH). It can be produced by crystallization. This manufacturing process typically uses an oxide molar ratio of Al ₂ O ₃ :1±0.5 R ₂ O ₅ :7 to 100 H ₂ O and at least about 1.5 moles of dihydroxide per mole of Al ₂ O ₃ . - forming a reaction mixture comprising n-propylamine. The reaction mixture is placed in a reaction vessel that is inert to the mixture and kept at a temperature of at least about 100°C, preferably from 100 to 300°C, for usually 2 hours to 2 weeks until crystallization.
heated at a temperature of The solid crystalline reaction product is then recovered by any convenient method such as filtration or centrifugation and dried in air at temperatures from ambient to about 110°C. A preferred crystallization method includes phosphoric acid as the phosphorus source, pseudo-boehmite hydrated aluminum oxide as the aluminum source, a temperature of 150-200°C, a crystallization time of 3-7 days, and an inorganic oxide in the reaction mixture. _The ratio _{is Al2O3} : _0.8-1.2P2O5 : _25-75H2O . A preferred templating agent is di-n-propylamine, present in an amount of about 1.5 to 2.0 moles per mole of alumina in the reaction mixture. Also, because of the relatively high concentration of basic amines, about 0.25 to 1.5 mole, preferably 0.5 to 1.0 mole, of an organic or mineral acid, such as acetic acid or hydrochloric acid, is present. Generally speaking, the stronger the acid, the lower its preferred concentration within the above range in the reaction mixture. In a preferred crystallization procedure, acetic acid is present in an amount of about 1 mole per mole of alumina and di-n-propylamine is present in an amount of about 2.0 moles per mole of alumina. Of note, di-n-propylamine has previously been used as a templating agent in the hydrothermal synthesis of another microporous crystalline aluminophosphate, AlPO ₄ -31. The synthesis of AlPO ₄ -31 is disclosed in US Pat. No. 4,385,994 (published on May 31, 1983).
It is written in However, in the synthesis,
Di-n-propylamine was present in the reaction mixture at a fairly low concentration, ie, 1 mole per mole of alumina, and no acid was added to the reaction mixture. From the available data, the amount of di-n-propylamine templating agent used can be reduced or eliminated, as long as pre-prepared AlPO ₄ -39 seed crystals are also present in the reaction mixture to influence the crystallization process. Even so, it appears that AlPO ₄ -39 can be synthesized appropriately. Containing as-synthesized templates of the present invention
AlPO ₄ -39 has a basic skeletal structure whose chemical composition expressed by the molar ratio of oxides is Al ₂ O ₃ :1.0±0.2P ₂ O ₅ and at least the d-spacing listed in the table below. Shows a characteristic X-ray powder diffraction pattern with:

【table】

[Table] All of the as-synthesized forms of AlPO ₄ -39 for which X-ray powder diffraction data have been obtained show the shapes within the general activity pattern in the table below:

[Table] The as-synthesized AlPO ₄ -39 composition can be calcined, that is, heated to a sufficiently high temperature, typically in the range of about 300°C to 700°C, or treated by other methods such as chemical oxidation to form crystals. When essentially all of the organic templating agent present within the internal pore system is removed, the composition exhibits an X-ray powder diffraction pattern having at least the d-spacing listed in Table A below:

【table】

[Table] All of the above X-ray figures and the following X-ray figures are
It can be obtained using standard X-ray powder diffraction techniques or by using computer-based techniques using a Siemens D-500 X-ray powder diffraction instrument available from Siemens Corporation of Cheery Hill, New Jersey. Using standard x-ray techniques, the radiation source is a high intensity copper target x-ray tube operated at 50 KV, 49 mA. Copper K-α
The radiation and diffraction patterns from the graphite monochromator are recorded by an X-ray spectrometer, scintillation counter, pulse height analyzer and strip chart recorder. Flat compressed powder sample 2 degrees (2 theta)/min
Scanning was performed using a constant time of 2 seconds. The distance between planes (d) (in Å) is 2〓 (theta)
The diffraction peak is obtained from the position of the diffraction peak observed on the striptchaat, where θ is the Bragg angle. Intensity was determined from the height of the diffraction peak after background subtraction. "Io" is the intensity of the stronger line or peak and "I" is the intensity of each of the other peaks. As understood by those skilled in the art, parameter 2〓
The determination of is subject to both human and machine error, independent of the technique used, and both these errors can impose an uncertainty of approximately 0.4° on each reported value of 2〓. Of course, this uncertainty is also reflected in the reported value of the d-spacing calculated from the 2〓 value. Such inaccuracies are generally art-wide and are not sufficient to exclude variations of the crystalline material of the present invention from prior art compositions. In some of the X-ray diagrams posted, the symbols VS, S, M, and W represent "very strong,""strong,""moderate," and "weak," respectively.
shows the relative strength of the d-spacing. _AlPO4-39 has surface properties that make it useful as a catalyst or catalyst support in a variety of hydrocarbon conversion and oxidative combustion processes. Then,
AlPO ₄ -39 can be combined with the catalytically active metal, for example, by skeletal substitution, impregnation, doping, etc., or by methods conventionally used in the industry for the production of catalyst compositions. It should be noted that AlPO ₄ -39 has a pore size of less than about 4.3 Å, making it suitable for use as a molecular sieve for the separation of molecular species. The following examples illustrate the invention in a non-limiting manner: Example 1 27.2 g of pseudo-boehmite phase hydrated aluminum oxide consisting of 75.1% by weight of Al ₂ O ₃ and 4.9% by weight of H ₂ O
85% by weight of orthophosphoric acid (H ₃ PO ₄ ) 46.2 and H ₂ O 46.2
AlPO ₄ -39 was produced by mixing g.
The resulting mixture was stirred until a homogeneity was observed. This mixture was then mixed with 12.1 g of glacial acetic acid (CH ₃ COOH) and stirred until homogeneous. 40.5 g of di-n-propylamine (n- _Pr2NH ) was added to this mixture and the resulting mixture was stirred again until homogeneous. The oxide molar ratio composition of _the reaction mixture was as follows: 2.0n- _Pr2NH : _{Al2O3 : P2O5} : _CH3COOH :
The 40H ₂ O reaction mixture was sealed in a polytetrafluoroethylene lined stainless steel pressure vessel and heated in a furnace at 150° C. under autogenous pressure for 168 hours.
The solid reaction product was collected by centrifugation, washed with water, and dried in air at ambient temperature. A portion of the solid reactant was chemically analyzed and the following results were obtained: wt% Carbon 8.0 Nitrogen 1.5 Al ₂ O ₃ 33.2 P ₂ O ₅ 45.9 Loss on ignition 21.6 The solid reaction product contained _a small _{amount of impurities} , but _the solid reaction product contained a small _{amount of} impurities.
The main phase exhibited an X-ray powder diffraction pattern characterized by the following data:

【table】

[Table] Example 2 (a) Same as Example 1 except that the crystallization time was 48 hours.
_AlPO4-39 was produced. The resulting solid reaction product was collected by centrifugation, washed with water, and dried in air at ambient temperature. The solid reaction product exhibited an X-ray powder diffraction pattern characterized by the following data:

[Table] (b) A portion of the reaction product is 4.75 at about 600℃ in the atmosphere.
Baked for an hour. The fired product is X listed in Table C below.
The line powder diffraction pattern was shown:

[Table] (c) The adsorption capacity for AlPO ₄ -39 [produced in (b) above] is the standard Mc Bain-Baqua (Mc Bain-
Bakr) was measured using a gravimetric adsorption device. The following data were obtained for the calcined sample of (b) above activated at 350°C:

[Table] From the above data, the pore size of the fired product is larger than about 3.46A as shown by oxygen (dynamic diameter 3.46A) adsorption and n-butane (dynamic diameter 3.46A).
4.3A) approximately 4.3Å as shown by non-adsorption
determined to be smaller. (d) The same sample used in the McBain-Bacqua gravimetric adsorption measurement in (c) above was analyzed for its X-ray powder diffraction pattern and was found to be characterized by the X-ray pattern listed in Table C above.

Claims (1)

[Scope of Claims] 1. Has a basic skeletal structure whose chemical composition expressed as a molar ratio of oxides is Al ₂ O ₃ :1.0±0.2P ₂ O ₅ , and has at least the following d-spacing d(A) relative A microporous crystalline aluminophosphate with a characteristic X-ray powder diffraction pattern comprising an intensity of 9.32-9.29 S 6.58 M 4.81-4.79 M 4.17-4.16 VS 3.88-3.89 VS 2.95-2.96 M. 2. It has a basic skeleton structure whose chemical composition expressed as a molar ratio of oxides is Al ₂ O ₃ :1.0±0.2P ₂ O ₅ and at least the following d
- a microporous crystalline aluminophosphate with a characteristic X-ray powder diffraction pattern containing a relative intensity of 9.32-9.29 S 6.58 M 4.81-4.79 M 4.17-4.16 VS 3.88-3.89 VS 2.95-2.96 M Microporous crystalline aluminophosphate resulting from calcination at temperatures of at least 300°C. 3. It has a basic skeleton structure whose chemical composition expressed by the molar ratio of oxides _{is Al2O3} :1.0± _0.2P2O5 , and at least the following d-spacing d( _A ) relative strength 9.28 W to M 6.53 A microporous crystalline amylnophosphate having a characteristic X-ray powder diffraction pattern comprising VS 4.65-4.76 W 4.14 W-M 3.82-3.93 W 3.06 W 3.02 W. 4 Has a basic skeletal structure whose chemical composition expressed as a molar ratio of oxides is Al ₂ O ₃ : 1.0±0.2P ₂ O ₅ and at least the following d
- spacing d(A) of a microporous crystalline aluminophosphate with a characteristic X-ray powder diffraction pattern containing a relative intensity of 9.32-9.29 S 6.58 M 4.81-4.79 M 4.17-4.16 VS 3.88-3.89 VS 2.95-2.96 M A manufacturing method,
It has the following composition expressed in oxide molar ratio: Al ₂ O ₃ : 1.0±0.5 P ₂ O ₅ : 7 to 100 H ₂ O, and about 1.5 to 2 mol of di-n-propyl per 1 mol of Al ₂ O ₃ per mole of amine and Al ₂ O ₃ approx.
by forming a reaction mixture containing 0.25 to 1.5 moles of organic or mineral acid and heating the reaction mixture thus formed at a temperature of at least 100° C. under autogenous pressure until crystals of said aluminophosphate form. A method. 5 Let the acid present in the reaction mixture be acetic acid, di-
5. The method of claim 4, wherein n-propylamine is present in _an amount of about 2 moles per mole of _Al2O3 .