CA2054604A1 - Crystalline aluminophosphates and related compounds - Google Patents

Crystalline aluminophosphates and related compounds

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Publication number
CA2054604A1
CA2054604A1 CA002054604A CA2054604A CA2054604A1 CA 2054604 A1 CA2054604 A1 CA 2054604A1 CA 002054604 A CA002054604 A CA 002054604A CA 2054604 A CA2054604 A CA 2054604A CA 2054604 A1 CA2054604 A1 CA 2054604A1
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Prior art keywords
crystalline
source
related compounds
aluminophosphates
process according
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.)
Abandoned
Application number
CA002054604A
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French (fr)
Inventor
David Michael Clark
Bettina Kraushaar-Czarnetzki
Ronald Jan Dogterom
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.)
Shell Canada Ltd
Original Assignee
David Michael Clark
Bettina Kraushaar-Czarnetzki
Ronald Jan Dogterom
Shell Canada Limited
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Application filed by David Michael Clark, Bettina Kraushaar-Czarnetzki, Ronald Jan Dogterom, Shell Canada Limited filed Critical David Michael Clark
Publication of CA2054604A1 publication Critical patent/CA2054604A1/en
Abandoned legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/82Phosphates
    • B01J29/84Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85Silicoaluminophosphates (SAPO compounds)
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/04Aluminophosphates (APO compounds)
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08Silicoaluminophosphates (SAPO compounds), e.g. CoSAPO
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00Chemistry of inorganic compounds
    • Y10S423/30Alpo and sapo

Abstract

A B S T R A C T

CRYSTALLINE ALUMINOPHOSPHATES
AND RELATED COMPOUNDS

Crystalline aluminophosphates and related compounds having in the as-synthesised dried form the chemical composition expressed as a R (b P205) (c A1203) (d SiO2) (e MeO) (z H2O) wherein R represents a diamine of the general formula wherein R1 represents a C8-C14 carbon chain which may contain one or more inert substituents and each of R2, R3, R4 and R5 represents a hydrogen atom or an alkyl group which may contain one or more inert substituents and Me represents a divalent metal moiety, wherein:
a:b = 0.5 - 1 (c + e):b = 0.4 - 0.95 d:b = 0 - 0.25 (c + e):a = 0.8 - 1.2 and z:b at least 0.1.
The compounds can be prepared from a forming solution or gel comprising a source of aluminium. a source of phosphorus, a source of a diamine as defined hereinabove and optionally a source of at least one metal moiety MeO, wherein the appropriate forming components are initially present in specific molar ratios and which mixture is kept at elevated temperature for a period of time sufficient to produce a crystalline aluminophosphate or related compound, followed by separating off the crystalline product obtained and drying, and which may subsequently be calcined.

Description

2~6~

CRYSTAL~INE ALUMINOPHOSPHATES
AND RELATED COMPOUNDS

The present invention relates to novel crystalline aluminophosphate compositions and a process for preparing such aluminophosphate compositions.
Crystalline aluminophosphate compositions are well known materials which find a promising reception in industry as new generations of molecular sieves, catalysts carriers as well as catalysts. For instance, in United States patent specification No. 4,310,440 the preparation of various crystalline aluminophosphates is described from reaction mixtures containing inter alia organic structure directing or templating agents including tetrapropylammonium hydroxide, quinuclidine, t-butylamine and ethylenediamine.
Classes of these materials comprise compositions crystallised in the AlPO4, SAPO4 (siliconaluminophosphate), MeAPO4 (metalloaluminophosphate) and ElAPO4 (non-metal substituted aluminophosphate) families.
It has now been found that novel crystalline aluminophosphates and related compounds, e.g. of the AlPO4-, SAPO4- and MeAPO4-type can be prepared from reaction gels or solutions when use is made of specific molar ratios of the appropriate forming components utilising certain organic diamines.
The present invention thus relates to crystalline aluminophosphates and related compounds having in the as-synthesised dried form the chemical composition expressed as:
( 25) (c A12O3) (d SiO2) (e MeO) (z H O) wherein R represents a diamine of the general formula wherein Rl represents a Cg-C14 carbon chain which may contain one or more inert substituents and each of R2, R3, R4 and R5 represents 2 9 ~

a hydrogen atom or an alkyl group which may contain one or morP
inert substituents and Me represents a divalent metal moiety, wherein a:b - 0.5 - 1 (c + e):b - 0.4 - 0.95 d:b - 0 - 0.25 (c + e):a - 0.8 - 1.2 and z:b at least 0.1.
A typical example of an inert substituent comprises a halogen atom, such as a fluorine atom.
In particular, the present invention relates to aluminophosphates and related compounds having the chemical composition as described hereinabove, wherein a:b - 0.5 - 1 (c + e):b - 0.5 - 0.9 d:b - 0 - 0.25 (c + e):a - 0.8 - 1.2 and z:b at least 0.2.
In an especially preferred embodi~ent of the present invention the ratio (c + e):b is 0.5 - 0.8.
The aluminophosphates and related compounds according to the present invention appear to possess a layered structure wherein the interlayer distances and the unit cell dimensions vary to some extent depending on the chain length of the diamine applied.
Particularly preferred organic diamine compounds within the scope of the present invention comprise those wherein Rl represents a C8-C12 carbon chain, in particular a C8 carbon chain, and each of R2, R3, R4 and R5 represents a hydrogen atom or a lower alkyl group. In particular, preference is given to 1,8-diaminooctane. It should be noted that the nitrogen atoms of the appropriate diaminoalkane each may carry a further hydrogen atom or lower alkyl group which necessitates the presence of anion(s) to cause electroneutrality.

~05~16~4 It should be understood that within the present specification a lower alkyl group is an alkyl group comprising 1 to 4 carbon atoms.
As divalent metal moiety Me can suitably be used one or more of beryllium, magnesium, manganese, iron, cobalt, zinc, nickel and chromium. Typically, said metal will be one or more of magnesium, manganese, iron, cobalt, zinc and nickel and preferably one or more of magnesium, manganese, cobalt and zinc. The presence of a divalent metal moiety in the novel compounds according to the present invention is optional, i.e. the value of e in the general formula as given hereinbefore can be zero. Normally, the percentage of e in the sum of c + e will not be more than 30~. In the event that e > O it will be appreciated that the as-synthesised form of the crystalline aluminophosphates and related compounds according to the present invention also contains an appropriate charge-balancing cation such as a proton or a protonic form of R as described hereinbefore.
It is well known to those skilled in the art that as-synthesised forms of crystalline aluminophosphates can contain traces of counterions originating from precursors of P205, A1203, SiO2 or MeO and/or traces of impurities.
SCS-22 is an example of a novel crystalline aluminophosphate according to the present invention which has been synthesised using 1,8-diaminooctane as template/structure directing agent. The characteristic lines of its X-ray diffraction pattern are given in Table I. When use is made of l,10-diaminodecane an SCS-22 type compound having the characteristic lines in its X-ray diffraction pattern as listed in Table II is obtained and when use is made of 1,12-diaminododecane an SCS-22 type compound having the characteristic lines of its X-ray diffraction pattern as listed in Table III is obtained.
The present invention also relates to novel crystalline aluminophosphates and related compounds which are substantially in the calcined, R-free form. Such compounds can be obtained by drying the as-synthesised materials and subjecting the dried materials to 2~5~Q~

an appropriate calcination to remove the template/structure directing agent substantially or totally The present invention also relates to a process for preparing novel crystalline aluminophosphates as well as related compounds as defined hereinbefore from a forming solution or gel comprising a source of aluminium, a source of phosphorus, optionally a source of at least one metal moiety MeO, and a source of a diamine as defined hereinbefore, which mixture is ~ept at elevated temperature for a period of time sufficient to produce a crystalline aluminophosphate or related compound followed by separating off the crystalline product obtained and drying, in which solution or gel the various components are initially present in the following molar ratios:

2 5 A123 > 1.3 and H2 A12O3 40 - 500, wherein Me and R have the meanings as defined hereinbefore.
The crystalline aluminophosphates and related compounds according to the present invention are preferably prepared from a forming solution or gel in which the various components are initially present in the following molar ratios :
R:Al O - O 15 - 2 MeO:Al2O3 - O - 2 P25 A123 - 1-5 - 2 5 and 2 2 3 3 0.
Crystalline aluminophosphates and related compounds according to the present invention having in the as-synthesised form an X-ray diffraction pattern containing at least the lines as given in Table I, II or III are suitably prepared from forming solutions or gels whilst keeping the temperature below 200 C, in particular at a temperature in the range of fsom 100 C to 200 C, most preferably in the range between 110 C and 180 C. The use of aqueous forming solutions or gels is preferred.
For preparing the forming solution or gel, any source or promoter form based on a diamine as defined hereinbefore can be 2~ 6~

used as template and/or structure directing agent, such as a quaternary ammonium compound of such diamine, which source or promoter should be such that it can be converted into the appropriate diamine.
The process according to the present invention can be carried out at autogenous pressure as well as at an elevated pressure.
Normally, the novel crystalline aluminophosphates and related compounds will be produced when the forming solution or gel has been kept under the appropriate conditions for a period of time allowing the proper structure to be formed.
Preferably, the process according to the present invention is carried out for a period of time ranging between 6 hours and 144 hours, in particular between 24 and 96 hours.
Examples of suitable aluminium sources comprise aluminium oxides, such as ~ and ~-alumina, hydroxides as well as mixtures thereof, such as gibbsite, boehmite and pseudo-boehmite or aluminium alkoxides, such as aluminium triisopropoxide.
Suitable phosphorus sources comprise phosphorus acids and derivatives thereof such as esters, phosphorus oxides, phosphates and phosphites, preferably phosphoric acids. Also mixtures of phosphorus sources can be applied.
Examples of suitable precursors of MeO comprise the appropriate chlorides, iodides, bromides, nitrates, sulphates and acetates.
It has been found that agitation, e.g. rotation, can be applied advantageously during crystallization to produce the desired crystalline aluminophosphates or related compounds from the forming solution or gel.
It should be noted that the expression "dried" as referred to in this specification should be understood to mean removal of physically adsorbed water. Normally, such removal will be achieved by exposing the as-synthesised material to a temperature regime of about 120 C for a period of time sufficient to substantially remove said water. Normally, such removal is achieved with a period of between 3 and 12 hours.

20~l~6~

The novel crystalline aluminophosphates and related compounds according to the present invention can be suitably used as molecular sieves, as catalysts or as catalyst carriers in the operation of various catalytic processes.
If desired, one or more (catalytically) active species, in particular protons and/or precursors thereof and/or one or more metal(s) (compounds) of Group III and/or th~ Transition Metals and/or Rare Earth Metals and/or precursors thereof, can be incorporated into the crystalline aluminophosphates and related compounds according to the present invention.
They can be incorporated by well-known techniques such as, for example, impregnation and ion-exchange.
The invention will now be illustrated by the following Examples.
Example_I
A crystalline SAP0, referred to as SCS-22, was prepared by mixing 10.2 grammes of aluminium triisopropoxide, 1.6 grammes of silica-sol (Ludox AS), 11.5 grammes of 85% H3P04, 7.2 grammes of C8DN (1,8 - diaminooctane) and 66.6 grammes of water giving a reaction gel mixture (on a molar basis) of 0.2 SiO2:0.5 A1203:1 P205:1 C8DN:80 H20.
This mixture was kept at 140 C for a period of 72 hours until a crystalline compound was obtained. After synthesis, the crystalline compound produced was separated from the reaction mixture by filtration, water washed and dried at 120 ~C.
The crystalline compound obtained has the following chemical composition, wherein R represents C8DN:
( 25) (0-88 A1203) (0-11 SiO2) (0-3 H 0) The characterising lines of its X-ray diffraction pattern are found within the ranges given in Table I below:

2~ 6~

Table I

d(A) Intensity 16.4 +/- 0.2 vs 12.4 +/- 0.2 vw 8.2 +/- 0.1 vw-wm 4.6 +/- 0.1 vw-w 4.27 +/- 0.05 vw-w 4.12 +/- 0.05 vw-w 4.09 +/- 0 05 vw-w 4.01 +/- 0.05 vw-w 3.96 +/- 0.05 vw-w 3.58 +/- 0.05 vw-w b 3.43 +/- 0.03 vw-w 3.26 +/- 0.03 vw-w b 3.09 +/- 0.03 vw-w 2.75 +/- 0.03 vw 2.72 +/- 0.03 vw Example II
The experiment described in the previous Example was repeated but using a smaller amount of silica-sol; so as to give a reaction gel mixture (on a molar basis) of 0.1 SiO2:0.5 Al203:1 P2O5:1 5C8DN:80 H20.
This mixture was kept at 140 C for 72 hours until a crystalline compound was obtained. After synthesis, the crystalline compound was separated from the reaction mixture by filtration, water washed and dried at 120 C.
The crystalline compound obtained has the following chemical composition, wherein R represents C8DN:
0-60 R (l P205) (0.92 Al203) ( 0.08 SiO2) (0.3 H20) and has an X-ray diffraction pattern consistent with that given in Table I.

2 ~

Example III
A crystalline SAPO, referred to as SCS-22, was prepared by mixing 51.1 gram~es of aluminium triisopropoxide, 11.7 grammes of SiliCA-Sol ~Ludox AS), 57.6 grammes of 85% H3PO4, 36.1 grammes of C8DN and 330.7 grammes of water giving a reaction gel mixture (on a molar basis) of 0.3 SiO2:0.5 A12O3:1 P2O5:1 C8DN:80 H2O.
This mixture was kept at 140 C for a period of 7 hours until a crystalline compound was obtained.
After synthesis, the crystalline compound produced was separated from the reaction mixture by filtration, water washed, and dried at 120 C. Its X-ray diffraction pattern is consistent with that given in Table I.
Example IV
A crystalline CoAPSO was prepared in an experiment which was carried out in a substantially analogous manner as described in Example III, by mixing 20.4 grammes of aluminium triisopropoxide, 4.7 grammes of silica-sol (Ludox AS), 23.1 grammes of 85% H3PO4, 14.4 grammes of C8DN, 130 grammes of H2O and additionally 7.5 grammes of Co(CH3COO)2.4H2O giving a reaction gel mixture (on a molar basis) of 0.3 SiO2:0.3 CoO:0.5 A12O3:1 P2O5:1 C8DN 80 H2O
This mixture was kept at 110 C for a period of 72 hours under gentle rotation until a crystalline compound was obtained. After synthesis, the crystalline compound produced was separated from the reaction mixture by filtration, water washed and dried at 120 C.
The crystalline compound has the following chemical composition wherein R represents C8DN:
) ( 25) (0-69 A12O3) (0-34 SiO2) (0-3 H O) and has an X-ray diffraction pattern consistent with that given in Table I.
Example V
The experiment described in the previous Example was repeated at a temperature of 140 C and using 3.7 grammes of pseudo-boehmite as the aluminium source.
After working up, an SCS-22 type CoAPSO was obtained having the following chemical composition, wherein R represents C8DN:

2~5~6~

0.66 R (0.25 CoO) (l P205) (0.75 Al203) (0.18 SiO2) (0.22 H20) and an X-ray diffraction pattern consistent with that given in Table I.
Example VI
The experiment described in the previous Example was repeated but using aluminium triisopropoxide as the aluminium source, a synthesis temperature of 120 C and an amount of cobalt (II) acetate tetrahydrate giving 0.2 mole of CoO per mole P205 in the starting reaction mixture.
After working up, an SCS-22 type CoAPSO was obtained having the following chemical composition, wherein R represents C8DN:
( 2 5) (0.61 A1203) (0-30 SiO2) (0-25 H O) and an X-ray diffraction pattern consistent with that given in Table I.
Example VII
The experiment described in the previous Example was repeated whilst stirring the reaction gel mixture for a period of 21.5 hours. After working up, a crystalline product was obtained having an X-ray pattern consistent with that given in Table I.
Example VIII
The experiment as described in Example IV was repeated at a temperature of 120 ~C for a period of 72 hours and using l,10-diaminodecane (ClODN) as the template/structure directing agent.
The crystalline compound obtained has the following chemical composition, wherein R represents ClODN:
) ( 25) (0.64 Al203) (0-41 SiO2) (0-3 H O) and has an X-ray diffraction pattern containing at least the lines given in Table II:

2 0 5 ~

Table II

d~A) Intensity 18.4 vs 9.2 w 4.59 vw 3.68 vw 3.06 vw Example IX
The experiment described in the previous Example was repeated but using 1,12-diaminododecane (C12DN) as template/structure directing agent.
The crystalline compound obtained hss the following chemical composition, wherein R represents C12DN:
0.94 R (0.42 CoO) (1 P2O5) (0.64 A1203) (0.37 SiO2) (0.3 H2O) and has an X-ray diffraction pattern containing at least the lines given in Table III:

Table III

d(A) Intensitv 20.2 vs 18.7 w 5.04 vw 4.03 vw 3.35 vw

Claims (16)

1. Crystalline aluminophosphates and related compounds having in the as-synthesised dried form the chemical composition expressed as:
a R (b P2O5) (c Al2O3) (d SiO2) (e MeO) (z H2O) wherein R represents a diamine of the general formula wherein R1 represents a C8-C14 carbon chain which may contain one or more inert substituents and each of R2, R3, R4 and R5 represents a hydrogen atom or an alkyl group which may contain one or more inert substituents and Me represents a divalent metal moiety, wherein a:b = 0.5 - 1 (c + e):b = 0.4 - 0.95 d:b = 0 - 0.25 (c + e):a = 0.8 - 1.2 and z:b at least 0.1.
2. Crystalline aluminophosphates and related compounds according to claim 1, wherein a:b = 0.5 - 1 (c + e):b = 0.5 - 0.9 d:b = 0 - 0.25 (c + e):a = 0.8 - 1.2 and z:b at least 0.2.
3. Crystalline aluminophosphates and related compounds according to claim 1 or 2, wherein R represents a C8-C12 carbon chain, in particular a C8 carbon chain, and wherein each of R2, R3, R4 and R5 represents a hydrogen atom or a lower alkyl group, preferably R
represents 1,8-diaminooctane.
4. Crystalline aluminophosphates and related compounds according to one or more of claims 1-3, wherein Me represents one or more of beryllium, magnesium, manganese, iron, cobalt, zinc, nickel and chromium, preferably one or more of magnesium, manganese, iron, cobalt, zinc and nickel, more preferably one or more of magnesium, manganese, cobalt and zinc.
5. Crystalline aluminophosphates and related compounds according to one or more of claims 1-4, whenever obtained in a substantially R-free form.
6. Crystalline aluminophosphates and related compounds according to one or more of claims 1-5, wherein one or more (catalytically) active species have been incorporated, preferably protons and/or precursors thereof and/or one or more metal(s) (compounds) of Group III and/or the Transition Metals and/or the Rare Earth Metals and/or precursors thereof.
7. A process for preparing crystalline aluminophosphates and related compounds according to claim 1 from a forming solution or gel comprising a source of aluminium, a source of phosphorus, optionally a source of at least one moiety MeO, and a source based on a diamine as defined hereinbefore, which mixture is kept at elevated temperature for a period of time sufficient to produce a crystalline aluminophosphate or related compound, followed by separating off the crystalline product obtained and drying, in which solution or gel the various components are initially present in the following molar ratios:
R:A1203 = 0.1 - 3 Me0:A1203 = 0 - 2 P205:A1203 = > 1.3 and H20:A1203 = 40 - 500.
8. A process according to claim 7, wherein the various components in the forming solution or gel are initially present in the following molar ratios:
R:Al203 = 0.15 - 2 MeO:A1203 = 0 - 2 P205:A1203 = 1.5 - 2.5 and H20:A1203 = 45 - 320.
9. A process according to claim 7 or 8, wherein use is made of an aluminium oxide, hydroxide and/or alkoxide as source of aluminium, in particular aluminium triisopropoxide.
10. A process according to one or more of claims 7-9, wherein use is made of phosphorus acids, phosphorus oxides, phosphates or phosphites as source of phosphorus.
11. A process according to one or more of claims 7-10, wherein use is made of a structure directing or template source as defined hereinbefore, wherein R1 represents a C8-C12 carbon chain and each of R2, R3, R4 and R5 represents a hydrogen atom or a lower alkyl group, preferably use is made of 1,8-diaminooctane.
12. A process according to one or more of claims 7-11, wherein use is made of a precursor of MeO in the form of the appropriate chlorides, iodides, bromides, sulphates, nitrates or acetates.
13. A process according to one or more of claims 7-12, wherein the temperature is kept below 200 °C, in particular in the range between 100 and 200 °C, and preferably in the range between 110 and 180 °C.
14. A process according to one or more of claims 7-13, wherein the forming solution or gel is kept for a period of time ranging between 6 and 144 hours, in particular between 24 and 96 hours, under crystal-forming conditions.
15. A process according to one or more of claims 7-14, wherein the crystalline product obtained is calcined.
16. A process for carrying out catalytic reactions, wherein use is made of a crystalline aluminophosphate or related compound according to one or more of claims 1-6.
CA002054604A 1990-11-02 1991-10-31 Crystalline aluminophosphates and related compounds Abandoned CA2054604A1 (en)

Applications Claiming Priority (2)

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US5370851A (en) * 1993-05-27 1994-12-06 Uop Crystalline silicoalumino phosphates: SAPO-36 and SAPO-56
US5405596A (en) * 1993-06-29 1995-04-11 Mobil Oil Corp. Synthesis of crystalline ZSM-23
US5514362A (en) * 1994-05-03 1996-05-07 Chevron U.S.A. Inc. Preparation of non-zeolitic molecular sieves
JP4313436B2 (en) * 1995-11-07 2009-08-12 シェブロン ユー.エス.エー. インコーポレイテッド Alumina sources for non-zeolitic molecular sieves
US5741751A (en) * 1995-11-07 1998-04-21 Chevron U.S.A. Inc. Alumina source for non-zeolitic molecular sieves
US6040264A (en) * 1996-04-04 2000-03-21 Exxon Chemical Patents Inc. Use of alkaline earth metal containing small pore non-zeolitic molecular sieve catalysts in oxygenate conversion
JP4054144B2 (en) * 1998-12-01 2008-02-27 協和化学工業株式会社 Hydrotalcite-based compounds in which some or all of the interlayer anions retain at least one anion of silicon-based, phosphorus-based and boron-based multimer oxygenate ions and other anions, their production method, and agricultural film use Infrared absorber and agricultural film containing the infrared absorber
US6927187B2 (en) * 2003-07-11 2005-08-09 Exxonmobil Chemical Patents Inc. Synthesis of silicoaluminophosphates
US6835363B1 (en) 2003-08-06 2004-12-28 Exxonmobil Chemical Patents Inc. Synthesis of molecular sieves of CHA framework type

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US4310440A (en) * 1980-07-07 1982-01-12 Union Carbide Corporation Crystalline metallophosphate compositions
US4440871A (en) * 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
NZ210467A (en) * 1983-12-19 1988-06-30 Mobil Oil Corp Crystalline silicophosphoaluminate material and its use as a catalyst
US4877593A (en) * 1988-03-10 1989-10-31 Mobil Oil Company Synthesis of crystalline aluminophosphate composition
WO1989008608A1 (en) * 1988-03-10 1989-09-21 Mobil Oil Corporation Synthetic crystalline molecular sieve and its synthesis
GB8813121D0 (en) * 1988-06-03 1988-07-06 Shell Int Research Novel crystalline aluminophosphates & related compounds
GB8914469D0 (en) * 1989-06-23 1989-08-09 Shell Int Research Novel crystalline aluminophosphates and related compounds
GB8924262D0 (en) * 1989-10-27 1989-12-13 Shell Int Research Novel crystalline aluminophosphates and related compounds
GB8926602D0 (en) * 1989-11-24 1990-01-17 Shell Int Research Novel crystalline aluminophosphates and related compounds

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JPH04285004A (en) 1992-10-09
EP0483927A2 (en) 1992-05-06
DE69120023D1 (en) 1996-07-11
DE69120023T2 (en) 1996-12-12
EP0483927B1 (en) 1996-06-05
EP0483927A3 (en) 1992-11-19

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