EP0442879A1 - Synthese d'un tamis moleculaire cristallin - Google Patents

Synthese d'un tamis moleculaire cristallin

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Publication number
EP0442879A1
EP0442879A1 EP89905323A EP89905323A EP0442879A1 EP 0442879 A1 EP0442879 A1 EP 0442879A1 EP 89905323 A EP89905323 A EP 89905323A EP 89905323 A EP89905323 A EP 89905323A EP 0442879 A1 EP0442879 A1 EP 0442879A1
Authority
EP
European Patent Office
Prior art keywords
mixture
aluminum
reaction mixture
phosphorus
molecular sieve
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP89905323A
Other languages
German (de)
English (en)
Inventor
Clarence Dayton Chang
John Dennis Lutner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mobil Oil AS
ExxonMobil Oil Corp
Original Assignee
Mobil Oil AS
Mobil Oil Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/179,175 external-priority patent/US5141728A/en
Priority claimed from US07/179,341 external-priority patent/US5147525A/en
Priority claimed from US07/179,344 external-priority patent/US5169614A/en
Application filed by Mobil Oil AS, Mobil Oil Corp filed Critical Mobil Oil AS
Publication of EP0442879A1 publication Critical patent/EP0442879A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/36—Aluminium phosphates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/04—Aluminophosphates [APO compounds]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO

Definitions

  • This invention relates to a method for synthesizing a crystalline molecular sieve having pore windows measuring greater than 10 Angstroms in diameter, such as, for example, greater than 12 Angstroms in diameter.
  • Zeolitic materials both natural and synthetic, have been demonstrated in the past to have catalytic properties for various types of hydrocarbon conversion.
  • Certain zeolitic materials are ordered, porous crystalline aluminosilicates having a definite crystalline structure as determined by »ray diffraction, within which there are cavities which may be interconnected by channels or pores. These cavities and pores are uniform in size within a specific zeolitic material. Since the dimensions of these pores are such as to accept for adsorption molecules of certain dimensions while rejecting those of larger dimensions, these materials have come to be known as "molecular sieves" and are utilized in a variety of ways to take advantage of these properties.
  • Patent 2,882,244 zeolite Y (U.S. Patent 3,130,007), zeolite ZK-5 (U.S. Patent 3,247,195), zeolite ZK-4 (U.S. Patent 3,314,752), zeolite ZSM-5 (U.S. Patent 3,702,886), zeolite ZSM-11 (U.S. Patent 3,709,979), zeolite ZSM-12 (U.S. Patent 3,832,449), zeolite ZSM-20 (U.S. Patent 3,972,983), zeolite ZSM-35 (U.S. Patent 4,016,245), zeolite ZSM-38 (U.S. Patent 4,046,859), and zeolite ZSM-23 (U.S. Patent 4,076,842).
  • zeolite Y U.S. Patent 3,130,007
  • zeolite ZK-5 U.S. Patent 3,247,195
  • zeolite ZK-4 U.S. Patent 3,314,752
  • Porous alu inophosphates and their synthesis with the aid of organic directing agents are disclosed in U.S. Patent Nos. 4,310,440 and 4,385,994, whereas the synthesis of silicophosphoaluminates of various structures are disclosed in U.S . Patents 4,440,871 and 4,673,559.
  • Methods for synthesizing crystalline etalloalur ⁇ inophosphates are described in U.S. Patent No. 4,713,227.
  • the present invention resides in a method for synthesizing a crystalline molecular sieve having an X-ray diffraction pattern with lines shown in Table 1A of the specification, which comprises (i) preparing a mixture comprising sources of oxides of aluminum, phosphorus, and optionally one or more elements (M) other than aluminum or phosphorus, water and a directing agent (DA), and having a composition, in terms of mole ratios, within the following ranges:
  • DA is a compound of the formula:
  • P, R 1 ', R 1 ' are the same or different and are selected from -Q- X and «-CH2CH2X, and X is a cation, (ii) maintaining said mixture under conditions including a temperature of 100°C to 145°C for a period of time of up to 80 hours and (iii) recovering the crystalline product from step (ii).
  • the crystalline molecular sieve produced according to the method of the invention has a framework topology which exhibits, even after being heated at 110°C or higher, a characteristic X-ray diffraction pattern having the following lines: Table 1A
  • the X-ray diffraction lines in Tables 1A, IB and 1C identify a crystal framework topology in the composition exhibiting large pore windows of 18-membered ring size.
  • the pores are at least
  • the X-ray pattern of the present composition is void of a d-spacing value at
  • the molecular sieve produced by the method of the invention comprises a three-dimensional framework structure composed of tetrahedral units of A10 2 , P0 2 and optionally MO , where M is at least one element other than aluminum or phosphorus . Where the element M is absent , the molecular sieve has the following composition , in terms of mole ratios of oxides :
  • M is preferably silicon alone , in which case the molecular sieve has the following composition in terms of mole ratios of oxides:
  • the molecular sieve will behave as a cation exchange material with potential use an an acidic catalyst.
  • the molecular sieve will behave as an anion exchange material with potential use as a basic catalyst.
  • silicon may also be present such that the ratio of silico :non-silicon atoms is less than 1, preferably less than 0.5.
  • the element M in this alternative embodiment has an oxidation number of from +2 to +6, and an ionic "Radius Patio" of 0.15 to 0.73, except that when the oxidation number of M is +2, the Radius Ratio of the element M is 0.52 to 0.62.
  • Radius Patio is defined as the ratio of the crystal ionic radius of the element M to the crystal ionic radius of
  • the crystalline composition will generally comprise structural aluminum, phosphorus and element M, and will exhibit an M/(aluminum plus phosphorus) atomic ratio of less than unity and greater than zero, and usually within the range of from 0.001 to 0.99.
  • the phosphorus/aluminum atomic ratio of such materials may be found to vary from 0.01 to 100.0, as synthesized. It is well recognized that aluminum phosphates exhibit a phosphorus/aluminum atomic ratio of about unity, and essentially no element M.
  • the phosphorus-substituted zeolite compositions sometimes referred to as "aluminosilicophosphate" zeolites, have a silicon/aluminum atomic ratio of usually greater than unity, and generally from 0.66 to 8.0, and a phosphorus/aluminum atomic ratio of less than unity, and usually from 0 to 1.
  • the molecular sieve described above is synthesized from a reaction mixture hydrogel containing sources of aluminum, phosphorus and optionally the non-aluminum, non- hosphorus element M, an organic directing agent, and water and having a composition, in terms of mole ratios, within the following ranges:
  • the directing agent DA is a compound represented by the formula:
  • R, R', R'' and R'' are the same as different and are selected from -CH ⁇ X and -CH ⁇ CH ⁇ X, and X is a cation such as hydroxide or halide (e.g. chloride or bromide).
  • X is a cation such as hydroxide or halide (e.g. chloride or bromide).
  • Preferred examples of these compounds include tetrakis (2-hydroxyethyl) ammonium hydroxide, tetrakis (2-chloroethyl)ammonium chloride and tetrakis(hydroxymethyl)ammonium bromide.
  • Reaction conditions involve heating the foregoing reaction mixture to a temperature of 100°C to 145°C for 1 hour to 80 hours.
  • a more preferred temperature range is from 130°C to 145°C with the amount of time at temperature being from 10 hours to 30 hours. If the temperature is higher than 145°C and/or the time exceeds 80 hours, the product composition will contain less of the des ' ired large pore crystals characterized by the X-ray diffraction patterns of Tables 1A, IB and 1C.
  • Also important in the synthesis procedure is the ratio of P 2 0-./Al 2 C- in the reaction mixture.
  • product composition will contain decreased amounts of the desired crystalline material.
  • the solid product composition comprising the desired molecular sieve is recovered from the reaction medium, such as by cooling the whole to room temperature, filtering and water washing.
  • the organic directing agent can then be removed from the product by conventional calcination procedures.
  • the synthesis method of the present invention is facilitated by the presence of seed crystals, such as those having the structure of the product crystals, in the reaction mixture.
  • seed crystals such as those having the structure of the product crystals
  • the use of at least 0.01%, preferably 0.10%, and even more preferably 1% seed crystals (based on total weight) of crystalline material in the reaction mixture will facilitate crystallization in the present method.
  • the reaction mixture composition for the present method is prepared utilizing materials which supply the appropriate oxide.
  • Useful sources of aluminum oxide include, as non-limiting examples, any known form of aluminum oxide or hydroxide, organic or inorganic salt or compound, e.g. alumina and aluminates. Such sources of aluminum oxide include pseudo-boehmite and aluminum tetraalkoxide.
  • Useful sources of phosphorus oxide include, as non-limiting examples, any known form of phosphorus acids or phosphorus oxides, phosphates and phosphites, and organic derivatives of phosphorus.
  • Useful sources of element M include, as non-limiting examples, any known form of non-aluminum, non-phosphorus element, e.g. metal, its oxide or hydride or salt, alkoxy or other organic compound containing M.
  • each oxide component utilized in the reaction mixture can be supplied by one or more essential reactants and they can be mixed together in any order.
  • any oxide can be supplied by an aqueous solution.
  • the reaction mixture can be prepared either batchwise or continuously. Crystal size and crystallization time for the product composition comprising the desired metalloaluminophosphate will vary with the exact nature of the reaction mixture employed within the above-described limitations.
  • the molecular sieve of the present invention may be used as an absorbent or as a catalyst component in a wide variety of organic compound, e.g. hydrocarbon compound, conversion reactions, it is notably useful as a catalyst in the processes of cracking, hydrocracking, isomerization and reforming.
  • Other conversion processes for which the present composition may be utilized as a catalyst component include, for example, dewaxing.
  • the crystalline molecular sieve prepared in accordance herewith can be used either in the as-synthesized form, the hydrogen form or another univalent or multivalent cationic form/ It can also be used in intimate combination with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed. Such components can be exchanged into the composition, impregnated therein or physically intimately admixed therewith.
  • a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed.
  • a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobal
  • Such components can be impregnated in or on to the crystalline composition such as, for example, by, in the case of platinum, treating the material with a platinum metal-containing ion.
  • Suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex. Combinations of metals and methods for their introduction can also be used.
  • the present composition when employed either as an adsorbent or as a catalyst in a hydrocarbon conversion process, should be dehydrated at least partially. This can be done by heating to a temperature in the range of from 65°C to 315°C in an inert atmosphere, such as air and nitrogen, and at atmospheric or subatmospheric pressures for between 1 and 48 hours. Dehydration can be performed at lower temperature merely by placing the zeolite in a vacuum, but a longer time is required to obtain a particular degree of dehydration.
  • the thermal decomposition product of the newly synthesized composition can be prepared by heating same at a temperature of from 200°C to 550°C for from 1 hour to 48 hours.
  • synthetic metalloaluminophosphate prepared in accordance herewith can have the original cations associated therewith replaced by a wide variety of other cations according to techniques well known in the art.
  • Typical replacing cations include hydrogen, ammonium and metal cations including mixtures thereof.
  • replacing metallic cations particular preference is given to cations of metals such as rare earths and metals from Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB AND VTII of the Periodic Table of Elements, especially Mh, Ca, Mg, Zn, Cd, Pd, Ni, Cu, Ti, Al, Sn, Fe and Co.
  • a typical ion exchange technique would be to contact the synthetic material with a salt of the desired replacing cation or cations.
  • a salt of the desired replacing cation or cations can be employed, particular preference is given to chlorides, nitrates and sulfates.
  • Such matrix materials include active and inactive materials and synthetic or naturally occurring zeolites as well as incorganic materials such as clays, silica and/or metal oxides, e.g. alumina. The latter maybe either naturally occurring or in the form of gelatinous precipitates, sols or gels including mixtures of silica and metal oxides.
  • an active material in conjunction with the present molecular sieve, i.e. combined therewith, may enhance the conversion and/or selectivity of the catalyst in certain organic conversion processes.
  • Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate or reaction.
  • crystalline catalytic materials have been incorporated into naturally occurring clays, e.g. bentonite and kaolin. These materials, i.e. clays, oxides, etc., function, in part, as binders for the catalyst. It is desirable to provide a catalyst having good crush strength, because in a petroleum refinery the catalyst is often subjected to rough handling, which tends to break the catalyst down into powder-like materials which cause problems in processing.
  • Naturally occurring clays which can be composited with the present molecular sieve include the montmorillonite and kaolin families which' include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays, or others in which the main mineral constituent is halloysite, kaolinite, dickite , nacrite or anauxite .
  • Such clays can be used in the raw state as originally mined or initially subjected to calcination , acid treatment or chemical modifi cation.
  • the crystals hereby synthes ized can be composited wi th a porous matrix material such as silica-alumina , silica -magnesia , silica-zirconia , silica -thoria , silica-beryllia , silica-ti tania , as well as ternary compos itions such as silica -alumina -thoria , s ilica-alumina-zirconia , silica -alumina -magnesia and silica-magnesia-z irconia.
  • the matrix can be in the form of a cogel . A mixture of these components could also be used .
  • the relative proportions of finely divided crystalline material and matrix vary widely wi th the crystall ine material content ranging from 1 to 90 percent by weight, and more usually in the range of 2 to 50 percent by weight of the composite .
  • reforming stocks can be reformed employing a temperature between 450 °C and 550 °C .
  • the pressure can be between 445 and 3550 kPa (50 and 500 psig) , but is preferably between 890 and 2170 kPa (100 and 300 psig) .
  • the liquid hourly space velocity is generally between 0.1 and 10 hr , preferably between 1 and 4 hr and the hydrogen to hydrocarbon mole ratio is generally between 1 and 10 , preferably between 3 and 5 .
  • a catalyst comprising the present composition can also be used for hydroisomerization of normal paraffins , when provided with a hydrogenation component , e .g . platinum.
  • Hydroisomerization is carried out at a temperature between 250 °C to 450 °C, preferably 300°C to 425°C , with a liquid hourly space velocity between 0 .1 and 10 hr ⁇ , preferably between 0.5 and 4 hr ⁇ , employing hydrogen such that the hydrogen to hydrocarbon mole ratio is between 1 and
  • the catalyst can be used for olefin or aroma tics isomerization employing temperatures between 0 °C and 556 °C.
  • a catalyst comprising the molecular seive of this invention can also be used for reducing the pour point of gas oils . This process is carried out at a liquid hourly space velocity between 0.1 and 5 hr" and a temperature between 300°C and 425°C.
  • Example 1 A mixture containing 103.5 g of 85% orthophosphoric acid (H,P0.) in 155 g water was mixed with 50.8 g aluminum oxide source (pseudo-boehmite). The mixture was heated to 8 °C with stirring for 1 hour. To this mixture was added 105.5 g tetrakis(2-hydroxyethyl)ammoniu ⁇ _ hydroxide (DA) in 150 g water, giving a final reaction mixture composed as follows:
  • the reaction mixture was placed in a 1000 cc autoclave. Crystallization in the autoclave was at 140°C under 2170 kPa (300 psig) nitrogen for 16 hours. The solid product was filtered, washed and dried. Washing was accomplished by extraction with water in a Soxhlet apparatus. The product was calcined at 538°C in air for 10 hours.
  • the reaction mixture was placed in a 1000 cc autoclave. Crystallization in the autoclave was at 142°C under 2170 kPa (300 psig) nitrogen for 17 hours. The solid product was filtered, washed and dried. Washing was accomplished by extraction with water in a Soxhlet apparatus. The product was calcined at 530°C in air for 10 hours.
  • the calcined product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 3 and Figure 2.
  • the reaction mixture was placed in an autoclave. Crystallization in the autoclave was at 138°C under 2170 kPa (300 psig) nitrogen for 14 hours. The solid product was filtered, washed and dried. Washing was accomplished by extraction with water in a Soxhlet apparatus. The product was calcined at 530°C in air for 10 hours.
  • a mixture containing 57.5 g of 85% orthophosphoric acid in 77.5 g water was mixed with 35.5 g aluminum oxide source (pseudo-boehmite). The mixture was heated to 80°C with stirring for 1 hour. To this mixture was added 52.75 g tetrakis(2-hydroxyethyl)ammonium hydroxide (DA) in 75 g water, giving a final reaction mixture composed as follows:
  • the calcined product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 4 and Figure 3.
  • the reaction mixture was placed in an autoclave. Crystallization in the autoclave was at 160°C under 2170 kPa (300 psig) nitrogen for 5 hours. The solid product was filtered, washed with water and dried.
  • the product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 5 and Figure 4.
  • Example 5 The product of Example 4, crystallized from the indicated reaction mixture at 160°C was found to be primarily A1P0.-5, void of any significant amount of the large pore aluminophosphate crystals of the present synthesis invention.
  • Example 5 The product of Example 4, crystallized from the indicated reaction mixture at 160°C was found to be primarily A1P0.-5, void of any significant amount of the large pore aluminophosphate crystals of the present synthesis invention.
  • the reaction mixture was placed in a 300 cc autoclave.
  • Crystallization in the autoclave was at 142°C under 2170 kPa (300 psig) nitrogen for 17 hours.
  • the solid product was filtered, washed and dried. Washing was accomplished by extraction with water in a
  • Soxhlet apparatus The product was calcined at 530°C in air for 10 hours.
  • the calcined product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of
  • a mixture containing 55 .8 g of 85% orthophosphoric acid (H,P0 4 ) in 77.5 g water was mixed with 35 .5 g aluminum oxide source (e .g . pseudo-boehmite ) and 1 .0 g silicon oxide source (e .g . HiSil ) .
  • the mixture was heated to 80 °C with stirring for 1 hour .
  • To this mixture was added 52.75 g tetrakis (2-hydroxyethyl )ammonium hydroxide (DA) in 75 g water , giving a final reaction mixture composed as follows :
  • the reaction mixture was placed in a 300 cc autoclave. Crystallization in the autoclave was at 151°C under 2170 kPa (300 psig) nitrogen for 20 hours. The solid product was filtered, wa nitrogen for 16 hours. The solid product was filtered, washed and dried at 110°C for 17 hours.
  • the product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 7 and Figure 6.
  • Example 6 The product of Example 6 , crystallized from the indicated reaction mixture at 151°C for 20 hours was primarily SAP0-5 and was void of any significant amount of the large pore silicoaluminophosphate crystals of the present synthesis invention .
  • Example 7 A mixture containing 56.6 g of 85% orthopbosphoric acid (H,P0, ) in 77.5 g water was mixed with 0.46 g of vanadium pentoxide (V-Or ) . The mixture was heated to 50°C with stirring for 30 minutes until complete dissolution of the vanadium pentoxide. Then, 35.5 g of aluminum oxide source (e.g . pseudo-boehmite) was added and the mixture was heated to 80 °C for 1 hour. To this mixture was added 52.75 g tetrakis ( 2- hydroxyethyDammoniu hydroxide (DA) in 75 g water, giving a final reaction mixture composed as follows:
  • the reaction mixture was placed in a 300 cc autoclave.
  • the reaction mixture was placed in a 300 cc autoclave. Crystallization in the autoclave was at 147°C at autogenous pressure for 17 hours. The solid product was filtered, washed with water and dried at 110°C for 17 hours.
  • Example 8 The product of Example 8 was composed primarily of crystals having the structure of AlP0 4 -5, with only a small amount of the large pore metalloaluminophosphate crystals of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Un procédé de synthèse d'un tamis moléculaire cristallin à gros pores, ayant une configuration de diffraction des rayons X avec les lignes caractéristiques (IA), consiste à (i) préparer un mélange comprenant des sources d'oxydes d'aluminium, de phospore, et facultativement un ou plusieurs éléments (M) différents de l'aluminium ou plusieurs éléments (M) différents de l'aluminium ou du phosphore, de l'eau ainsi qu'un agent d'orientation (DA), dont la composition exprimée en rapports molaires se situe dans les plages suivantes: M/Al2O3 0 à 0,5; P2O5/Al2O3 0,5 à 1,25; H2O/Al2O3 10 à 100; DA/Al2O3 0,5 à 1,5; DA est un composé de la formule (I), dans laquelle R, R', R'' et R''' sont identiques ou différents et sont choisis parmi -CH2-X1-CH2CH2X, et X est un cation; (ii) maintenir ledit mélange dans certaines conditions comprenant une température de 100°C à 145°C pendant une période de temps allant jusqu'à 80 heures et (iii) récupérer le produit cristallin de l'étape (ii).
EP89905323A 1988-04-08 1989-03-31 Synthese d'un tamis moleculaire cristallin Withdrawn EP0442879A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US07/179,175 US5141728A (en) 1988-04-08 1988-04-08 Synthesis of crystalline aluminophosphate composition
US179344 1988-04-08
US179341 1988-04-08
US07/179,341 US5147525A (en) 1983-12-19 1988-04-08 Synthesis of crystalline metalloaluminophosphate composition
US07/179,344 US5169614A (en) 1988-04-08 1988-04-08 Synthesis of crystalline silicoaluminophosphate composition
US179175 1994-01-10

Publications (1)

Publication Number Publication Date
EP0442879A1 true EP0442879A1 (fr) 1991-08-28

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EP89905323A Withdrawn EP0442879A1 (fr) 1988-04-08 1989-03-31 Synthese d'un tamis moleculaire cristallin

Country Status (7)

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EP (1) EP0442879A1 (fr)
JP (1) JPH03503881A (fr)
KR (1) KR900700385A (fr)
AU (1) AU3549189A (fr)
DK (1) DK279590D0 (fr)
NZ (1) NZ228425A (fr)
WO (1) WO1989009749A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0464249B1 (fr) * 1990-07-05 1994-01-05 VAW Aluminium AG Procédé pour préparer des tamis moléculaires cristallins à grands pores
FR2671790B1 (fr) * 1991-01-18 1993-04-16 Inst Francais Du Petrole Procede de preparation de composes aluminophosphates et derives substitues de type structural vfi invention de : jean-francois joly, herve cauffriez et jean-louis guth.
GB0222477D0 (en) * 2002-09-27 2002-11-06 British Nuclear Fuels Plc Novel ion-exchange materials
CN102530987A (zh) 2010-12-29 2012-07-04 中国科学院大连化学物理研究所 Sapo分子筛的溶剂热合成方法及由其制备的催化剂
US9637392B2 (en) 2012-05-24 2017-05-02 Tosoh Corporation Silicoaluminophosphate, method for producing the same, and solid acid catalyst comprising the same

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Publication number Priority date Publication date Assignee Title
JPH03505720A (ja) * 1987-08-28 1991-12-12 ザ　ダウ　ケミカル　カンパニー 結晶性アルミニウムホスフェート組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8909749A1 *

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DK279590A (da) 1990-11-23
WO1989009749A1 (fr) 1989-10-19
JPH03503881A (ja) 1991-08-29
KR900700385A (ko) 1990-08-13
AU3549189A (en) 1989-11-03
DK279590D0 (da) 1990-11-23
NZ228425A (en) 1990-11-27

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