WO1989009748A1 - Synthesis of a crystalline molecular sieve - Google Patents
Synthesis of a crystalline molecular sieve Download PDFInfo
- Publication number
- WO1989009748A1 WO1989009748A1 PCT/US1989/001353 US8901353W WO8909748A1 WO 1989009748 A1 WO1989009748 A1 WO 1989009748A1 US 8901353 W US8901353 W US 8901353W WO 8909748 A1 WO8909748 A1 WO 8909748A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mixture
- aluminum
- phosphorus
- molecular sieve
- reaction mixture
- Prior art date
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 23
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 title description 6
- 238000003786 synthesis reaction Methods 0.000 title description 5
- 239000000203 mixture Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910001868 water Inorganic materials 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 150000004820 halides Chemical group 0.000 claims abstract description 4
- 239000011541 reaction mixture Substances 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 2
- BZOHHLMTCXVRJE-UHFFFAOYSA-N 2-(hydroxymethyl)-1,3-dihydroinden-2-ol Chemical compound C1=CC=C2CC(CO)(O)CC2=C1 BZOHHLMTCXVRJE-UHFFFAOYSA-N 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 12
- 239000011148 porous material Substances 0.000 abstract description 8
- 229910052593 corundum Inorganic materials 0.000 abstract description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- 239000010457 zeolite Substances 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 229910021536 Zeolite Inorganic materials 0.000 description 14
- 150000001768 cations Chemical class 0.000 description 14
- 239000013078 crystal Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- -1 alkaline earth metal cation Chemical class 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000002178 crystalline material Substances 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 150000003017 phosphorus Chemical class 0.000 description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010011416 Croup infectious Diseases 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical group O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940000425 combination drug Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 201000010549 croup Diseases 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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]
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 X»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.
- Such molecular sieves include a wide variety of positive ion--containing crystalline aluminosilicates.
- These aluminosilicates can be described as rigid three-dimensional frameworks of SiO * and A10, in which the tetrahedra are cross--1inked by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen atoms is 1:2.
- the electrovalence of the tetrahedra containing aluminum is balanced by the inclusion in the crystal of a cation, for example an alkali metal or an alkaline earth metal cation.
- Patent 2,882,244 zeolite Y (U.S. Patent 3,130,007), zeolite ZK-5 (U.S. Patent 3,247,195), zeolite Z -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 ZS -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 Z -4 U.S. Patent 3,314,752
- 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:
- PA is a compound of the formula:
- 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:
- the X-ray diffraction lines in Tables 1A, IE- and 1C identify a crystal framework topology in the composition exhibiting large pore windows of 18-membered ring size.
- the pores are at least 10 Angstroms in diameter, such as for example at least 12 Angstroms, e.g. 12-13 Angstroms, in diameter.
- These lines distinguish this topology from other crystalline aluminosilicate, aluminophosphate and silicoaluminophosphate structures.
- the X-ray pattern of the present composition is void of a d-spacing value at 13.6-13.3 Angstroms with any significant intensity relative the strongest d-spacing value. If a d-spacing value in this range appears in a sample of the present composition, it is due to impurity and will have a weak relative intensity.
- this X-ray diffraction pattern is characteristic of all the species of the present compositions. Ion exchange of cations with other ions results in a composition which reveals substantially the same X-ray diffraction pattern with some minor shifts in interplanar spacing and variation in relative intensity. Pelative intensity of individual lines may also vary relative the strongest line when the composition is chemically treated, such as by dilute acid treatment. Other variations can occur, depending on the composition component ratios of the particular sample, as well as its degree of thermal treatment. The relative intensities of the lines are also susceptible to changes by factors such as sorption of water, hydrocarbons or other components in the channel structure. Further, the optics of the X-ray diffraction equipment can have significant effects on intensity, particularly in the low angle region. Intensities may also be affected by preferred crystallite orientation.
- the molecular sieve produced by the method of the invention comprises a three-dimensional framework structure composed of tetrahedral units of A10-,, P0 2 and optionally MO-,, where M is at least one element other than aluminum or phosphorus. Where the element V 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: where x is 0.5 to 1 .5 , y is 0 .01 to 0.5 and n is 0-100 and preferably 0-10.
- the molecular sieve When z is greater than 0, the molecular sieve will behave as a cation exchange material with potential use an an acidic catalyst. When z is less than 0, the molecular sieve will behave as an anion exchange material with potential use as a basic catalyst. In some cases silicon may also be present such that the ratio of silicon: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.
- Padius Ratio is defined as the ratio of the crystal ionic radius of the element M to the crystal ionic radius of
- Examples of elements not included as M of the present invention include:
- the crystalline composition will generally comprise structural aluminum, phosphorus and element :', 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
- 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. Also, the phosphorus-substituted zeolite compositions,
- 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.
- reaction mixture hydrogel containing sources of aluminum, phosphorus and optionally the non-aluminum, non-phosphorus 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 is selected from -F, -CF 3 X, -CF 2 C 2 X and combinations thereof
- R ' is selected from -CH ⁇ X, -CF 2 CH 2 X and combinations thereof
- X is hydroxide , halide (e.g . chloride or bromide ) , amino or a comb ination thereof .
- Preferred examples of these compounds include 2 -amino-2- (hydroxymethyl)-l ,3-propanediol ;
- Reaction condi tions involve heating the foregoing reaction mixture to a temperature of 100°C to 160°C for 1 hour to 80 hours .
- a more preferred temperature range is from 130 °C to 150 °C with the amount of time at temperature being from 5 hours to 80 hours . If the temperature is hi gher than about 160 °C and/or the time exceeds about 80 hours , the product composition will contain less of the desired large pore crystals characterized by the X-ray diffraction patterns of Tables 1A, I B and lC . Al so important in the synthesis procedure is the ratio of r , r/Al 2 0-, in the reaction mixture . When the ratio P n 0--/Al 9 0, is greater than about
- 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.
- 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, 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.
- 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 a ine complex. Combinations of
- 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 re ⁇ uired 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 Croups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB AND VIII of the Periodic Table of Elements, especially Mn, Ca, Mg, Zn, d, Pd, ⁇ 'i, 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.
- salts can be employed, particular preference is given to chlorides, nitrates and sulfates.
- 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 may be 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 prsent molecular sieve include the mont orillonite 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 modification.
- the crystals hereby synthesized can be composited with a porous matrix material such as silica -alumina, silica -magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica -titania, as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
- 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 with the crystalline material content ranging from 1 to 90 percent by weight, and more usually in 5 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 0 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 5 used for hydroisomerization of normal paraffins, when provided with a hydrogenation component, e.g. platinum.
- Fydroisomerization is carried out at a temperature between 250°C to 450°C, preferably
- the catalyst can be used for olefin or aromatics isomerization employing temperatures between 0°C and 550°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 115 g of 85% or tho phosphoric acid (F,P0. ) in 155 g water was mixed with 67.7 g aluminum oxide source (e .g . pseudo-boehmite) . The mixture was heated to 80°C with stirring for 3 hours . To this mixture was added 60.5 g 2-amino-2-(hydroxymethyl ) -l ,3-propanedi l (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 133 °C under 2170 kPa (300 ps ig) 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 . -
- the 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 a 300 cc autoclave. Crystallization in the autoclave was at 143°C at autogenous pressure for 16 hours. The solid product was filtered, washed with water and dried at 110°C overnight.
- the product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 4 and Figure 3.
- reaction mixture was placed in a 300 cc autoclave. 1D Crystallization in the autoclave was at 145 °C at autogenous pressure for 16 hours. The solid product was filtered, washed with water 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 5 and -3 Figure 4.
- the reaction mixture was placed in a 300 cc autoclave. Crystallization in the autoclave was at 140°C at autogenous pressure 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.
- the calcined product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 6 and the Figure 5.
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Abstract
A method for synthesizing a large pore crystalline molecular sieve having an X-ray diffraction pattern with lines shown in Table 1A of the specification 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: M/Al2O3 0 to 0.5; P2O5/Al2O3 0.5 to 1.25; H2O/Al2O3 10 to 100; DA/Al2O3 0.5 to 1.5, wherein DA is a compound of formula (I), wherein R is selected from -H, -CH2X, -CH2CH2X and combinations thereof, R' is selected from -CH3X, -CH2CH2X and combinations thereof, and X is hydroxide, halide, amino or a combination thereof, (ii) maintaining said mixture under conditions including a temperature of 100°C to 160°C for a period of time of up to 80 hours and (iii) recovering the crystalline product from step (ii).
Description
- l -
SYNTHESIS OF A CRYSTALLINE MOLECULAR SIEVE
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 X»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.
Such molecular sieves, both natural and synthetic, include a wide variety of positive ion--containing crystalline aluminosilicates. These aluminosilicates can be described as rigid three-dimensional frameworks of SiO* and A10,, in which the tetrahedra are cross--1inked by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen atoms is 1:2. The electrovalence of the tetrahedra containing aluminum is balanced by the inclusion in the crystal of a cation, for example an alkali metal or an alkaline earth metal cation. This can be expressed wherein the ratio of aluminum to the number of various cations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity. Che type of cation may be exchanged either entirely or partially with another type of cation utilizing ion exchange techniques in a conventional manner. By means of such cation exchange,. it is possible to vary the properties of a given aluminosilicate by suitable selection of the cation.
Prior art techniques have resulted in the formation of a great variety of synthetic zeolites. The zeolites have come to be designated by letter or other convenient symbols, as illustrated by zeolite A (U.S. Patent 2,882,243), zeolite X (U.S. Patent 2,882,244), zeolite Y (U.S. Patent 3,130,007), zeolite ZK-5 (U.S. Patent 3,247,195), zeolite Z -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 ZS -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).
Porous alu inophosphates and their synthesis with the aid of organic directing agents are disclosed in U.S. Patent bs. 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 4,67-3,559. Methods for synthesizing crystalline metalloaluminophosphates 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:
M/A1203 0 to 0.5
P2O5/AI2O3' 0.5 to 1.25 '
H2°/Al2θ3 10 to 100
DA/AI2.O3 0.5 to 1.5 wherein PA is a compound of the formula:
■ N-C
wherein R is selected from =-F, -CH-.X, --CH-CH C and combinations thereof, R' is selected from --CH-rX, -CK CF^X and combinations thereof, and X is hydroxide, halide, amino or a combination thereof, (ii) maintaining said mixture under conditions including a temperature of 10 °C to 160°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
Interplanar d-Spacings (A) Relative Intensity
16.4 +_ 0.2 vs 8 .2 +• 0.1 w
4.74 +_ 0.05 w
and more specifically- the following characteris tic values :
Tabl e IB
Interplanar d-Spacings (A) Relative Intensity
16.4 +_ 0.2 vs
8 .2 + 0.1 w 6.21
1 6 .17)1 0.05 w
5 .48 +_ 0.05 w
4.74 +. 0.05 w and even more specifically the following characteristic values:
1 rable 1C
Interplanar d-Spacings (A) Relative Intensity 16.4 + 0.2 vs
8.2 T 0.1 w
5.48 + 0.05 w
4.74 + 0.05 w
4.10 + 0.04 w
4.05 ^ 0.04 w
3.76 + 0.03 w
3.28 + 0.03 w
The X-ray diffraction lines in Tables 1A, IE- and 1C identify a crystal framework topology in the composition exhibiting large pore windows of 18-membered ring size. The pores are at least 10 Angstroms in diameter, such as for example at least 12 Angstroms, e.g. 12-13 Angstroms, in diameter. These lines distinguish this topology from other crystalline aluminosilicate, aluminophosphate and silicoaluminophosphate structures. It is noted that the X-ray pattern of the present composition is void of a d-spacing value at 13.6-13.3 Angstroms with any significant intensity relative the strongest d-spacing value. If a d-spacing value in this range appears in a sample of the present composition, it is due to impurity and will have a weak relative intensity.
These X-ray diffraction data were collected with conventional X-ray systems, using copper K-alpha radiation. The positions of the peaks, expressed in degrees 2 theta, where theta is the Bragg angle, were determined by scanning 2 theta. The interplanar spacings, d, measured in Angstrom units (A), and the relative intensities of the lines, I/I0. where I is one-hundredth of the intensity of the strongest line, including subtraction of the background, were derived. The relative intensities are given in terms of the symbols vs = very strong (75-100%), s = strong (50-74%), = medium (25-49%) and w = weak (0-249_). It should be understood that this X-ray diffraction
pattern is characteristic of all the species of the present compositions. Ion exchange of cations with other ions results in a composition which reveals substantially the same X-ray diffraction pattern with some minor shifts in interplanar spacing and variation in relative intensity. Pelative intensity of individual lines may also vary relative the strongest line when the composition is chemically treated, such as by dilute acid treatment. Other variations can occur, depending on the composition component ratios of the particular sample, as well as its degree of thermal treatment. The relative intensities of the lines are also susceptible to changes by factors such as sorption of water, hydrocarbons or other components in the channel structure. Further, the optics of the X-ray diffraction equipment can have significant effects on intensity, particularly in the low angle region. Intensities may also be affected by preferred crystallite orientation.
More specifically, the molecular sieve produced by the method of the invention comprises a three-dimensional framework structure composed of tetrahedral units of A10-,, P02 and optionally MO-,, where M is at least one element other than aluminum or phosphorus. Where the element V is absent, the molecular sieve has the following composition, in terms of mole ratios of oxides:
Al203:xP205:nH?0 where x is 0.5 to 1.5, and n is 0-100 and preferably 0-10.
Where present, M is preferably silicon alone, in which case the molecular sieve has the following composition in terms of mole ratios of oxides:
where x is 0.5 to 1 .5 , y is 0 .01 to 0.5 and n is 0-100 and preferably 0-10.
Al ternatively M includes an element other than silicon , such that the sum of the aluminum and phosphorus exceeds the number
of M atoms and the molecular sieve has the following composition, in the anhydrous state and in terms of mole ratios of oxides: CA10 l.χ-fre l-y* (M°r together with anions and/or cations necessary for electrical neutrality, where m is the valence (or weighted average valence) of M, x and y satisfy the following relationship: z = y - x +(4 + m) . (x + y) and z is greater than -1 and less than +1. When z is greater than 0, the molecular sieve will behave as a cation exchange material with potential use an an acidic catalyst. When z is less than 0, the molecular sieve will behave as an anion exchange material with potential use as a basic catalyst. In some cases silicon may also be present such that the ratio of silicon: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.
The term "Padius Ratio" is defined as the ratio of the crystal ionic radius of the element M to the crystal ionic radius of
,2 the oxygen anion, 0 .
Radius Patio = crystal ionic radius of the element M crystal ionic radius of Q7"^
The crystal ionic radii of elements are listed in the CRC
Handbook of Chemistry and Physics, 61st edition, CRC Press, Inc.,
1980, pages F-216 and F-217. In determining the Padius Ratio, it is necessary to use crystal ionic radii of the M atom and oxygen anion
(0' ) which have been measured by the same method.
Examples of element M useful herein include:
M Valence Radius Ratio
As +3 0.44
B +3 0.17
Bi +3 0.73
Co +2 0.55
Cu +2 0.54
Fe +2 0.56
Fe +3 0.48
Ge +2 0.55
Ge +4 0.40
In +3 0.61
Mn +2 0.61
Sb +3 0.57
Sn +4 0.54
Ti +3 0.58
Ti +4 0.52
V +3 0.56
V +4 0.48
V +5 0.45
Zn +2 0.56
Examples of elements not included as M of the present invention include:
Flement Valence Padius Patio
+1 0.26
Ea +1 1.16 Ba +2 1.02 Ce +3 0.78 Cd +1 0.86 Cd +2 0.73 Cr +1 0.61 Cr +2 0.67 Cu +1 0.73 La +1 1.05 Mg +1 0.62 Mg +2 0.50 Mo +1 0.70 Sn +2 0.70 Sr +2 0.85 Th +4 0.77 Ti +1 0.73 Ti +2 0.71 Zn +1 0.67
As synthesized, the crystalline composition will generally comprise structural aluminum, phosphorus and element :', 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
5 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. Also, the phosphorus-substituted zeolite compositions,
-1-0 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.
According to the invention, the molecular sieve described
1-5 above is synthesized from a reaction mixture hydrogel containing sources of aluminum, phosphorus and optionally the non-aluminum, non-phosphorus element M, an organic directing agent, and water and having a composition, in terms of mole ratios, within the following ranges:
20
Broad Preferrred Most Preferred
P2O5/AI7O3 0.5 to 1.25 0.9 to 1.1 0.9 to 1.1
H20/A1203 ' 10 to 100 20 to 80 30 to 60
DA/A1203 0.5 to 1.5 0.7 to 1.3 0.9 to 1.1 t. and when the element M is present:
M/AI2O3 0.01 to 0.5 0.01 to 0.2 0.01 to 0.1
The directing agent DA is a compound represented by the formula:
wherein R is selected from -F, -CF3X, -CF2C 2X and combinations thereof , R ' is selected from -CH^X, -CF2CH2X and combinations thereof , and X is hydroxide , halide (e.g . chloride or bromide ) , amino or a comb ination thereof . Preferred examples of these compounds include 2 -amino-2- (hydroxymethyl)-l ,3-propanediol ;
2-amino-2- (hydroxyethyl )-l ,3-propanediol ; 2 -amino-2- (chloromethyl ) -l ,3-propanedio l ; and 2- [bis (2-hydroxyethyl )amino] -2- (hydroxymethyl )-l ,3-propanediol .
Reaction condi tions involve heating the foregoing reaction mixture to a temperature of 100°C to 160°C for 1 hour to 80 hours .
A more preferred temperature range is from 130 °C to 150 °C with the amount of time at temperature being from 5 hours to 80 hours . If the temperature is hi gher than about 160 °C and/or the time exceeds about 80 hours , the product composition will contain less of the desired large pore crystals characterized by the X-ray diffraction patterns of Tables 1A, I B and lC . Al so important in the synthesis procedure is the ratio of r, r/Al20-, in the reaction mixture . When the ratio Pn0--/Al90, is greater than about
1.25, especially if the temperature is higher than 160°C, 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. 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.
It will be understood that 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. For example, 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.
While 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. 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 a ine 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 reαuired 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. As above mentioned, 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. Of the replacing metallic cations, particular preference is given"to cations of metals such as rare earths and metals from Croups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB AND VIII of the Periodic Table of Elements, especially Mn, Ca, Mg, Zn, d, Pd, \'i, 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. Although a wide variety of salts can be employed, particular preference is given to chlorides, nitrates and sulfates. When used as a catalyst, it may be desirable to incorporate the molecular sieve of the invention with another material resistant to the temperatures and other conditions employed in organic conversion processes. 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 may be either naturally occurring or in the form of gelatinous precipitates, sols or gels including mixtures of silica and metal oxides. Use of 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. Freαuently, 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 prsent molecular sieve include the mont orillonite 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 modification.
In addition to the foregoing materials, the crystals hereby synthesized can be composited with a porous matrix material such as silica -alumina, silica -magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica -titania, as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. 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 with the crystalline material content ranging from 1 to 90 percent by weight, and more usually in 5 the range of 2 to 50 percent by weight of the composite.
Employing a catalyst comprising the molecular sieve of this invention containing a hydrogenation component, 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 0 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 5 used for hydroisomerization of normal paraffins, when provided with a hydrogenation component, e.g. platinum. Fydroisomerization 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 -1 , preferabl -between 0.5 and 4 hr -1 , employing hydrogen such that the hydrogen to hydrocarbon mole ratio is between 1 and
10. Additionally, the catalyst can be used for olefin or aromatics isomerization employing temperatures between 0°C and 550°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.
This invention will now be more particularly described with reference to the Examples and the accompanying drawings in which Figures 1-5 are X-ray diffraction patterns of the calcined product of Examples 1 to 5 respectively.
Example 1 A mixture containing 115 g of 85% or tho phosphoric acid (F,P0. ) in 155 g water was mixed with 67.7 g aluminum oxide source (e .g . pseudo-boehmite) . The mixture was heated to 80°C with stirring for 3 hours . To this mixture was added 60.5 g 2-amino-2-(hydroxymethyl ) -l ,3-propanedi l (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 133 °C under 2170 kPa (300 ps ig) 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 . -
The calcined product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 2 and Figure 1.
Table 2
Interplanar Observed Relative d-Spacings (A) 2xTheta Intensities (I/In)
16.40867 5.386 100.0
8.19406 10.797 22.0
6.22941 14.218 9.1
4.91983 18.030 1.3
4.72564 18.778 10.5
4.11821 21.579 30.1
4.09145 21.721 42.6
-1.08315 21.766 47.0
4.07624 21.803 44
4.06619 21.858 38
3.97326 22.376 27
3.96098 22.446 29
. 3.75925 23.668 11
3.27174 27.257 19.1
3.15857 28.254
3.06849 29.102 0.5
3.03410 29.439 0.7
3.00716 29.709 0.1
2.74326 32.643
2.73029 32.802
Fxample 2
A mixture containing 43.13 g of 85% orthophosphoric acid (H,P0.) in 58.13 g water was mixed with 26.63 g aluminum oxide source (e.g. pseudo-boehmite). The mixture was heated to 80°C with stirring for 1 hour. To this mixture was added 39.23 g 2-[bis(2-hydroxyethyl)amino]-2- (hydroxymethyl)-l,3-propanediol(DA) in 56.3 g water, giving a final reaction mixture composed as follows:
P2°5'/A12°3 1 H20/A1203 38
DA/A1203 1
The reaction mixture was placed in a 300 cc autoclave. Crystallization in the autoclave was at 139°C at autogenous pressure for 17 hours. The solid product was filtered, washed with water 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 3 and Figure 2.
Table 3
Interplanar Observed Relative d-Spacings (A) ZxTheta Intensities (I/In)
16.51973 5.350 100.0
9.71099 9.107 8.4
8.23988 10.737 35.4
6.87604 12.875 36.2
6.51008 13.602 26.0
6.19219 14.304 20.9
5.47369 16.193 5.4
4.88634 18.155 18.5
4.84931 18.295 19.5
4.74462 18.702 25.2
4.25858 20.859 30.6
4.09396 21.708 90.3
3.97009 22.394 76.7
3.76893 23.606 36.7
3.65771 24.334 7.7
3.39887 26.219 13.2
3.28028 27.185 40.4
3.16209 28.222 8.5
3.09066 28.888 16.3
3.06583 29.127 28.0
2.94961 30.302 23.5
2.89852 30.849 ' 20.1
2.77916 32.209 10.2
2.73832 32.703 17.6
2.68422 53.381 11.1
Fxample 3
A mixture containing 57.5 g of 85% ortho phosphoric acid (F P0 ) in 77.5 g water was mixed with 35.5 g aluminum oxide source (e.g. pseudo-boehmite). The mixture was heated to 80°C with stirring for 1 hour. To this mixture was added 30.29 g 2-amino-2-(hydroxymethyl)-l,3-propanediol (DA) in 75 g water, giving a final reaction mixture composed as follows:
P205/Al7θ3 = 1
H2O/AI-.O3 = 40
DA/A1203 = 1
The reaction mixture was placed in a 300 cc autoclave. Crystallization in the autoclave was at 143°C at autogenous pressure for 16 hours. The solid product was filtered, washed with water and dried at 110°C overnight.
The product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 4 and Figure 3.
Table 4
Interplanar Cfc served Relative d-Spacings (A) 2xTheta Intensities (I/Ip)
16.40302 5.388 100.0
14.55986 6.070 6.8
8.13625 10.874 20.6
5.86246 15.113 1.6
5.04921 17.565 3.4
4.77368 18.587 7.4
4.72421 18.784 6.6
4.11681 21.586 97.1
4.08501 21.756 61.4
3.98676 22.299 66.2
3.94881 22.516 60.1
3.72953 23.859 8.8
3.72359 23.897 9.1
3.71147 23.977 5.7
3.60682 24.683 2.0
3.57887 24.879 2.2
3.53667 25.181 0.6
3.50296 25.427 1.3
3.47204 25.657 1.0
3.46064 25.743 3.2
3.43435 25.944 3.4
3.28415 27.153 3.8
3.16004 28.241 2.5
3.12045 28.606 2.5
3.10055 28.794 0.7
3.09072 28.888 2.7
3.03520 29.428 1.8
2.98502 29.934 1.4
2.95882 30.205 6.1
2.91584 30.661 3.2
2.90715 30.755 3.0
2.83916 31.511 1.6
2.82203 31.707 0.4
2.78326 32.161 2.7
2.70790 33.081 1.6
2.60406 34.440 2.8
2.58906 34.646 1.0
Exa ple 4 A mixture containing 50.7 g of 85% orthophosphoric acid (H,P04) in 69.75 g water was mixed with 32 g aluminum oxide source (e.g. pseudo-boehmite) and 0.54 g silicon oxide source (Cab-0-Sil). The mixture was heated to 80 °C with stirring for 2 hours. To this mixture was added 67.5 g water and 27.26 g 2-amino-2-(hydroxymethyl)-l ,3-propanediol (DA), giving a final reaction mixture composed as follows:
10
Si07/Al203 = 0.05
P705/A1703 = 1
H20/Al-.03 = 41
DA/A1203 = 1
The reaction mixture was placed in a 300 cc autoclave. 1D Crystallization in the autoclave was at 145 °C at autogenous pressure for 16 hours. The solid product was filtered, washed with water 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 5 and -3 Figure 4.
Table 5
Interplanar Observed Relative d-Spacings (A) 2xTheta Intensities (i/ι0 )
16.38220 5.394 100.0
8.21040 10.775 18.0
6.17347 14.347 29.1
4.73743 18.731 14.6
4.38766 20.239 0.9
4.09495) 21.703 46.6 4.073653 21.817 56.5
3.95601) 22.475 39.0 3.94952) 22.512 43.1
3.76970 23.601 18.7
3.64326 24.432 5.9
3.48219 25.581 0.8
3.40984 26.134 • 1.4
3.28336 27.159 24.9
3.17003 28.150 10.0
3.16060 28.235 9.3
3.09154 28.880 11.9
2.95432 30.252 17.6
2.94884 30.310 13.3
2.90777 30.749 8.0
2.89643 30.872 8.8
2.78136 32.183 4.3
2.76632 52.363 8.2
2.74021 32.680 15.2
2.65871 33.711 0.3 Example 5
A mixture containing 56.6 g of 85% orthophosphoric acid (FjP04) in 77.5 g water was mixed with 0.46 g of vanadium pentoxide (V_,05). The mixture was heated to 50°C with stirring for about 30 minutes until complete dissolution of the vanadium pentoxide. Then 33.9 g of aluminum oxide source (e.g. pseudo-boehmite) was added and the mixture was heated to °C for 3 hours. To this mixture was added 75 g water and 30.25 g 2-amino-2-
(hydroxymethyl)-l ,3-propanediol (DA), giving a final reaction mixture composed as follows:
/AI2O3 = 0.01
P205/A1203 = 1
F20/A1203 == 40
DA/A1203 = 1
The reaction mixture was placed in a 300 cc autoclave. Crystallization in the autoclave was at 140°C at autogenous pressure 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.
The calcined product was analyzed by X-ray powder diffraction and found to be crystalline and to show the pattern of Table 6 and the Figure 5.
Table 6
Interplanar Observed Relative d-Spacings (A) 2xTheta Intensities (I/Ip)
19.83167 4.456 2.7
16.43141 5.378 80.4
14.05582 6.288 10.3
8.96756 9.863 21.1
8.26906 10.699 10.5
6.14841 14.406 7.6
5.55584 15.952 2.1
5.45132 16.260 2.1
4.44238 19.987 9.7
4.21637 21.070 4.5
4.10532 21.647 100.0
3.96423 22.427 45.1
3.93916 22.572 57.3
3.91247 22.728 36.6
3.84869 23.110 8.2
3.80145 23.401 7.1
3.76941 23.603 11.7
3.75995 23.663 12.3
3.64396 24.428 3.1
3.61512 24.626 0.0
3.56765 24.959 9.5
3.54561 25.116 14.4
3.39630 26.240 2.4
3.27957 27.191 9.7
3.18955 27.974 1.2
3.16754 28.172 1.3
3.11576 28.650 1.3
3.08362 28.956 1.5
3.03104 29.469 11.0
3.00753 29.705 8.6
2.95816 30.212 1.2
2.94305 30.371 0.9
2.90184 30.813 0.7
2.81792 31.755 1.4
2.73526 32.741 2.9
2.65071 33.816 0.2
2.61667 34.269 1.3
Claims
1 . A method for synthesiz ing a crystalline molecular sieve having an X-ray diffraction pattern with l ines 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 :
wherein DA is a compound of the formula :
wherein P is selected from -F, -CH?X, -CH2CF2X and combinations thereof, P' is selected from -CF J,X, -CF L-,CF?X and combinations thereof, and X is hydroxide, halide, amino or a combination thereof, (ii) maintaining said mixture under conditions including a temperature of 100°C to 160°C for a period of time of up to 80 hours and (iii) recovering the crystalline product from step (ii).
2. The method of claim 1 wherein M is present in the reaction mixture and M/A120, is 0.01 to 0.5.
3. The method of claim 1 wherein the mixture has the following composition ranges:
P205/A1203 0.9 to 1.1
H20/A1203 20 to 80 PA/A120, 0.7 to 1.3
4. The method of claim 3 wherein M is present in the reaction mixture and M/Al^O, is 0.01 to 0.2
5. The method of Claim 1 wherein said mixture has the following composition ranges:
P2°5 A1203 ° '9 t0 1 Λ
H20/A120 30 to 60
DA/A1?03 0.9 to 1.1
6. The method of claim 5 wherein M is present in the reaction mixture and M/Al->0, is 0.01 to 0.1
7. The method of claim 2 wherein M includes an element other than silicon having an oxidation number +2 and an ionic radius ratio of 0.52 to 0.62 or an oxidation number of +3 to +6 and an ionic radius ratio of 0.15 to 0.73.
8. The method of claim 2 wherein M includes In +,
_, 4+ c 4+ „.3+ „.4+ Sb , Sn , Ti or Ti .
9. The method of claim 2 , wherein M also includes silicon such that the ratio of silicon:non-silicon atoms in the M0? component is less than 1.
10. The method of claim 1 wherein the directing agent DA is 2 -am__no- 2- (hydroxymethyl) -1 ,3-propanediol or
2 - [bis (2- (hydroxymethyl )amino ] - 2- (hydroxymethyl ) -1 , 3 -propanediol .
Priority Applications (2)
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---|---|---|---|
KR1019890702289A KR900700384A (en) | 1988-04-08 | 1989-12-07 | Synthesis method of crystalline molecular sieve |
DK279490A DK279490A (en) | 1988-04-08 | 1990-11-23 | PREPARATION OF A CRYSTALLIC MOLECULE SIGLE MATERIAL |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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US07/179,343 US5141729A (en) | 1988-04-08 | 1988-04-08 | Synthesis of crystalline metalloaluminophosphate composition |
US07/179,173 US5147626A (en) | 1988-04-08 | 1988-04-08 | Synthesis of crystalline aluminophosphate composition |
US179,173 | 1988-04-08 | ||
US179,331 | 1988-04-08 | ||
US179,343 | 1988-04-08 |
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WO1989009748A1 true WO1989009748A1 (en) | 1989-10-19 |
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PCT/US1989/001353 WO1989009748A1 (en) | 1988-04-08 | 1989-03-31 | Synthesis of a crystalline molecular sieve |
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EP (1) | EP0408664A1 (en) |
JP (1) | JPH03503631A (en) |
AU (1) | AU3533789A (en) |
WO (1) | WO1989009748A1 (en) |
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FR2671790A1 (en) * | 1991-01-18 | 1992-07-24 | Inst Francais Du Petrole | PROCESS FOR THE PREPARATION OF ALUMINOPHOSPHATE COMPOUNDS AND SUBSTITUTED DERIVATIVES OF STRUCTURAL TYPE VFI INVENTION OF: JEAN-FRANCOIS JOLY, HERVE CAUFFRIEZ AND JEAN-LOUIS GUTH |
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IL77747A (en) * | 1986-01-31 | 1991-07-18 | Plastro Gvat | Water sprinkler |
Citations (1)
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WO1989001912A1 (en) * | 1987-08-28 | 1989-03-09 | The Dow Chemical Company | Crystalline aluminumphosphate compositions |
-
1989
- 1989-03-31 AU AU35337/89A patent/AU3533789A/en not_active Abandoned
- 1989-03-31 WO PCT/US1989/001353 patent/WO1989009748A1/en not_active Application Discontinuation
- 1989-03-31 EP EP89905341A patent/EP0408664A1/en not_active Withdrawn
- 1989-03-31 JP JP1504743A patent/JPH03503631A/en active Pending
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WO1989001912A1 (en) * | 1987-08-28 | 1989-03-09 | The Dow Chemical Company | Crystalline aluminumphosphate compositions |
Non-Patent Citations (2)
Title |
---|
Nature, vol. 331, no. 6158, 25 February 1988, (London, GB) M.E. Davis et al.: "A molecular sieve with eighteen-membered rings" pages 698-699 * |
Zeolites, vol. 8, September 1988, (Guildford, GB) M.E. Davis et al.: "VPI-5: the first molecular sieve with pores larger than 10 Angstromes" pages 362-366 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2671790A1 (en) * | 1991-01-18 | 1992-07-24 | Inst Francais Du Petrole | PROCESS FOR THE PREPARATION OF ALUMINOPHOSPHATE COMPOUNDS AND SUBSTITUTED DERIVATIVES OF STRUCTURAL TYPE VFI INVENTION OF: JEAN-FRANCOIS JOLY, HERVE CAUFFRIEZ AND JEAN-LOUIS GUTH |
EP0496647A1 (en) * | 1991-01-18 | 1992-07-29 | Institut Français du Pétrole | Method for preparation of aluminophosphate compounds and substituted derivatives of VFI structural type |
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AU3533789A (en) | 1989-11-03 |
JPH03503631A (en) | 1991-08-15 |
EP0408664A1 (en) | 1991-01-23 |
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