WO1989005775A1 - Crystalline molecular sieve - Google Patents
Crystalline molecular sieve Download PDFInfo
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- WO1989005775A1 WO1989005775A1 PCT/US1988/004482 US8804482W WO8905775A1 WO 1989005775 A1 WO1989005775 A1 WO 1989005775A1 US 8804482 W US8804482 W US 8804482W WO 8905775 A1 WO8905775 A1 WO 8905775A1
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- Prior art keywords
- composition
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 8
- 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 8
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 19
- 239000002178 crystalline material Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- -1 tetrapropylammonium compound Chemical class 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical group CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 150000001767 cationic compounds Chemical class 0.000 claims description 2
- 229910001411 inorganic cation Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 16
- 239000010457 zeolite Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910021536 Zeolite Inorganic materials 0.000 description 13
- 150000001768 cations Chemical class 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000011148 porous material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 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
- 239000007788 liquid Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000005265 dialkylamine group Chemical group 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- SSNCHIVTFFFALV-UHFFFAOYSA-E P(=O)([O-])([O-])[O-].[W+4].[Ca+2].[Al+3].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[W+4].[Ca+2].[Al+3].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-] SSNCHIVTFFFALV-UHFFFAOYSA-E 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 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
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 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
- 238000010420 art technique Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 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
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052744 lithium 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
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals 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
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 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
- 150000003017 phosphorus Chemical class 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/04—Aluminophosphates [APO compounds]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
Definitions
- This invention relates to a synthetic crystalline " molecular sieve composition and in particular to a composition containing a framework +3 valence element, e.g. aluminum, a framework +5 valence element, e.g. phosphorous, and preferably a framework +4 valence element, e.g. silicon.
- a framework +3 valence element e.g. aluminum
- a framework +5 valence element e.g. phosphorous
- a framework +4 valence element e.g. silicon.
- 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-linked 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.
- cation exchange it has been possible to vary the properties of a given aluminosilicate by suitable selection of the cation.
- 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 Z -5 (U.S. Patent 3,247,195), zeolite ZK-4 (U.S. Patent 3,314,752), zeolite ZSM-5 (U.S. Patent 3,702,886), zeolite ZSM-11 (U.S. Patent
- zeolite ZSM-12 U.S. Patent 3,832,449
- zeolite ZSM-20 U.S. Patent 3,972,983
- zeolite ZSM-35 U.S. Patent 4,016,245)
- zeolite ZSM-38 U.S. Patent 4,046,859
- zeolite ZSM-23 U.S. Patent 4,076,842
- Aluminum phosphates are taught in, for example U.S.
- 3,213,035 teaches improving hardness of aluminosilicate catalysts by treatment with phosphoric acid.
- the catalysts are amorphous.
- the present invention resides in a novel synthetic crystalline molecular sieve composition
- a novel synthetic crystalline molecular sieve composition comprising at least 70% by weight of a crystalline material having the X-ray diffraction lines listed in Table 1A below: and more specifically the following X-ray diffraction lines:
- 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. Relative intensity of individual lines may 5 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 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.
- 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 line at a d-spacing of 6.19 +_ 0.07A is believed to be a doublet at 6.21 +_ 0.05A and 6.17 + 0.05A but in many cases the doublet is difficult to resolve.
- the X-ray diffraction lines in Tables 1A and IB identify a crystal framework topology exhibiting large pore windows of 0 18-membered ring size.
- the pores are at least 12 Angstroms, e.g. 12-13 Angstrom, in diameter.
- the crystalline framework of the composition of this invention has the general chemical formula:
- X is a +3 valence element
- Y is a +5 valence element
- Z is an optional +4 valence element
- x and y are each greater than -1 and less than +1, with anions and/or cations being present as 0 necessary for electrical neutrality.
- the element Z is present and x and y satisfy the further relationships:
- the +3 valence element x is preferably selected from aluminum, iron, chromium, vanadium, molybdenum, arsenic, antimony, manganese, gallium and boron;
- the +4 valence element Z is preferably selected from silicon, germanium and titanium;
- the .+5 valence element Y is preferably selected from phosphorous, arsenic, antimony and vanadium.
- X is aluminum, Y is phosphorus and Z is silicon.
- the composition can be a cation exchange material with potential use as an acidic catalyst, or it can be an anion exchange material with potential use as a basic catalyst.
- composition of the present invention is prepared by providing a reaction mixture comprising sources of X oxide, Y oxide and Z oxide, water, an organic directing agent B, inorganic cations M and. anions N, the components of said reaction mixture having the following relationship:
- d/(d+2c+2e) is up to 0.2 (preferably 0.05 to 0.2)
- a/(d+2c+2e) is 0.2 to 0.4, and preferably the addition relationships: b/(c+d+e) is less than 2, c ⁇ e g/(c- ⁇ l+e) is less than 2, and h/(c+d+e) is from 3 to 150,
- the initial pH of the reaction mixture should be 4-6.
- the mixture is heated with agitation to a temperature of 130 to 155°C and maintained at this temperature until crystals of oxide material are formed.
- the pH is controlled during the reaction so that the final pH is 6-7 and the reaction to produce at least 70%, and preferably at least 80% of the composition of the invention (based on the weight of the total crystalline phase) is normally complete after 4-20 hours.
- the crystalline product is recovered by separating same from the reaction medium, such as by cooling the whole to room temperature, filtering and washing with water before drying.
- a two-phase reaction mixture in which at least one of the X, Y and Z oxides is dissolved or dispersed in an organic solvent.
- the above reaction mixture composition can be prepared from any suitable materials which supply the appropriate components.
- Useful sources of +3 valence element, e.g. aluminum include any known form of oxide or hydroxide, organic or inorganic salt or compound.
- Useful sources of +4 valence element, e.g. silicon include, any known form of dioxide or silicic acid, alkoxy- or other compounds of such element.
- Useful sources of +5 valence element, e.g. phosphorus include, any known form of phosphorus acids or phosphorus oxides, phosphates and phosphites, and organic derivatives of such element.
- the organic solvent is a Cr-C, 0 alcohol or any other liquid compound substantially immiscible with water.
- the organic directing agent can be an organic mono- or dialkylamine, with alkyl being of 3 or 4 carbon atoms, or an onium compounds having the following formula:
- R or R 1 is alkyl of from 1 to 20 carbon atoms , or combinations thereof ;
- M is a tetra coordinate element (e.g . nitrogen, phosphorus , arsenic, antimony or bismuth) ;
- X is an anion (e .g. fluoride , chloride , bromide , iodide, hydroxide , acetate , sulfate, carboxylate) .
- Particularly preferred directing agents include tetraethylammonium hydroxide , tetra propylammonium bromide or most preferably tetrapropylammonium hydroxide and dialkylamines wherein alkyl is butyl or most preferably propyl.
- the temperature must be carefully controlled within the 130 - 155°C range specified abaove. The preferred temperature within this range depends on the directing agent employed, so that with 5 dipropyla ine the preferred temperature is 135 - 155°C, most preferably about 150°C, whereas with tetrapropylammonium hydroxide the preferred temperature is 130 - 145°C, preferably about 135°C.
- the present composition will also contain occluded organic directing agent and water molecules, 1° entrapped during the synthesis and filling the icroporous voids. However, these can be removed by heating.
- the original cations of the as-synthesized present composition can be replaced in accordance with techniques well known in the art, at least in part, by ion exchange with other cations.
- I 5 Preferred replacing cations include metal ions, hydrogen ions, hydrogen precursor, e.g. ammonium, ions and mixtures thereof.
- Particularly preferred cations are those which render the composition catalytically active or control catalytic activity, especially for hydrocarbon conversion. These include hydrogen, rare
- a typical ion exchange technique would be to contact the synthetic present composition with a salt of the desired replacing cation or cations.
- salts include the halides, e.g.
- the crystalline composition of the present invention can be beneficially thermally treated, either before or after ion exchange.
- This thermal treatment is performed by heating the composition in an atmosphere such as air, nitrogen, hydrogen, steam, 0 etc., at a temperature of from 300°C to 1100°C, preferably from 350°C to 750°C, for from 1 minute to 20 hours. While subatmospheric or superatmospheric pressures may be used for this thermal treatment, atmospheric pressure is desired for reasons of convenience. It may be desirable to incorporate the new composition with another material, i.e. a matrix, resistant to the temperatures and other conditions employed in various organic conversion processes.
- Such materials include active and inactive material and synthetic or naturally occurring zeolites as well as inorganic 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 or gels including mixtures of silica and metal oxides.
- Catalyst compositions containing the present composition will generally comprise from 1% to 90% by weight of the present composition and from 10% to 99% by weight of the matrix material. More preferably, such catalyst compositions will comprise from 2% to 80% by weight of the present composition and from 20% to 98% by weight of the matrix.
- Inactive materials suitably serve as diluents to cont--ol 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 of reaction.
- These materials may be incorporated into naturally occurring clays, e.g. bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions.
- Said materials, i.e. clays, oxides, etc. function as binders for the catalyst. It may be desirable to provide a catalyst having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials.
- Naturally occurring clays which can be composited with the new crystal include the montmorillonite and kaolin families which include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
- the present composition can be composited with a porous matrix material such as aluminum phosphate, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alu ina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia.
- the relative proportions of finely divided crystalline material and inorganic oxide gel matrix vary widely, with the crystal content ranging from 1 to 90 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of 2 to 80 weight percent of the composite.
- reforming stocks can be reformed employing a temperature of 370°C to 540°C, a pressure of 100 psig to 1000 psig (791 to 6996 kPa), preferably from 200 psig to
- a liquid hourly space velocity is of 0.1 to 10, preferably 0.5 to 4, and a hydrogen to hydrocarbon mole ratio of 1 to 20, preferably 4 to 12.
- a catalyst comprising the present composition can also be used for hydroisomerization of normal paraffins, when provided with a hydrogenation component, e.g. platinum.
- a hydrogenation component e.g. platinum.
- Such hydroisomerization is carried out at a temperature of 90°C to 375°C, preferably 145°C to 290°C, with a liquid hourly space velocity of 0.01 to 2, preferably 0.25 to 0.50, and with a hydrogen to hydrocarbon mole ratio of 1:1 to 5:1.
- a catalyst can be used for olefin or aromatic isomerization, employing a temperature of 200°C to 480°C.
- Such a catalyst can also be used for reducing the pour point of gas oils. This reaction is carried out at a liquid hourly space velocity of 10 to 30 and at a temperature of 425°C to 595°C.
- a catalyst comprising the composition of this invention containing a metal, e.g. platinum
- a metal e.g. platinum
- hydrogenation-dehydrogenation reactions and desulfurization reactions include hydrogenation-dehydrogenation reactions and desulfurization reactions, olefin polymerization (oligomerization) and other organic compound conversions, such as the conversion of alcohols (e.g. ethanol) or ethers (e.g. dimethylether) to hydrocarbons, and the alkylation of aromatics (e.g. benzene) in the presence of an alkylating agent (e.g. ethylene).
- alcohols e.g. ethanol
- ethers e.g. dimethylether
- aromatics e.g. benzene
- an alkylating agent e.g. ethylene
- Figure 1 shows the X-ray diffraction pattern of the as-synthesized Example 1 product
- Figure 2 shows the X-ray diffraction pattern of the calcined Example 1 product
- Figure 3 shows the X-ray diffraction pattern of the as-synthesized Example 3 product
- Figure 4 shows the X-ray diffraction pattern of the calcined Example 3 product.
- EXAMPLE 1 A two-phase synthesis reaction mixture was prepared with the organic phase comprising lOg Si (OC 2 H 5 ) 4 and 60g 1-hexanol, and the aqueous phase comprising 23g H,P0 4 (85%), 14g A1 2 0 3 , lOg di-n-propylamine (DPA) and 60g of H 2 0.
- the reaction mixture as a whole had the following approximate composition:
- the crystalline product was separated from the reaction mixture by filtration, washed with toluene and ether and then dried. A sample of the product was then submitted for X-ray analysis and found to be a crystalline composition exhibiting the diffraction lines shown in Table 2A. The X-ray diffraction pattern of this sample is shown in Figure 1. This product, after calcination at 450°C in nitrogen and air for four hours each, was found to have the X-ray pattern shown in Table 2B and Figure 2.
- Example 2 The process of Example 1 was repeated but with the reaction mixture being heated at 50°C/hour to 130°C, maintained at this temperature for 24 hours , heated to 200°C, and then maintained at this temperature for 24 hours .
- the composition having the X-ray lines listed in Tables 1A and B was present, it constituted less than 70% by weight of the overall crystalline product .
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Abstract
A synthetic crystalline molecular sieve composition comprises at least 70 % by weight of a crystalline material having the following X-ray diffraction lines:
Description
-1-
CRYSTALLINE MOLECULAR SIEVE
This invention relates to a synthetic crystalline"molecular sieve composition and in particular to a composition containing a framework +3 valence element, e.g. aluminum, a framework +5 valence element, e.g. phosphorous, and preferably a framework +4 valence element, e.g. silicon.
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-linked 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 has been 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 Z -5 (U.S. Patent 3,247,195), zeolite ZK-4 (U.S. Patent 3,314,752), zeolite ZSM-5 (U.S. Patent 3,702,886), zeolite ZSM-11 (U.S. Patent
3,709,979), zeolite ZSM-12 (U.S. Patent 3,832,449), zeolite ZSM-20 (U.S. Patent 3,972,983), zeolite ZSM-35 (U.S. Patent 4,016,245), zeolite ZSM-38 (U.S. Patent 4,046,859), and zeolite ZSM-23 (U.S. Patent 4,076,842). Aluminum phosphates are taught in, for example U.S.
Patents 4,310,440 and 4,385,994.
Silicoaluminophosphates of various structure are taught in U.S. Patent 4,440,871. U.S. Patent 4,363,748 describes a combination of silica and aluminu -calciu -cerium phosphate as a low acid activity catalyst for oxidative dehydrogenation. Great Eritain Patent 2,068,253 discloses a combination of silica and aluminum-calcium-tungsten phosphate as a low acid activity catalyst for oxidative dehydrogenation. U.S. Patent 4,228,036 teaches an alumina-aluminum phosphate-silica matrix as an amorphous body to be mixed with zeolite for use as cracking catalyst. U.S. Patent
3,213,035 teaches improving hardness of aluminosilicate catalysts by treatment with phosphoric acid. The catalysts are amorphous.
The present invention resides in a novel synthetic crystalline molecular sieve composition comprising at least 70% by weight of a crystalline material having the X-ray diffraction lines listed in Table 1A below:
and more specifically the following X-ray diffraction lines:
Table IB
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 (75-1001), s = strong (50-74%), = medium (25-49%) and w = weak (0-24%). 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. Relative intensity of individual lines may 5 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 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. F rther, 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. In addition, the line at a d-spacing of 6.19 +_ 0.07A is believed to be a doublet at 6.21 +_ 0.05A and 6.17 + 0.05A but in many cases the doublet is difficult to resolve.
The X-ray diffraction lines in Tables 1A and IB identify a crystal framework topology exhibiting large pore windows of 0 18-membered ring size. The pores are at least 12 Angstroms, e.g. 12-13 Angstrom, in diameter.
The crystalline framework of the composition of this invention has the general chemical formula:
5 + (X0 ) :(Y0 ) :(Z0 ) 2 1-y 2 1-x 2 x+y wherein X is a +3 valence element, Y is a +5 valence element, Z is an optional +4 valence element, and x and y are each greater than -1 and less than +1, with anions and/or cations being present as 0 necessary for electrical neutrality. Preferably, the element Z is present and x and y satisfy the further relationships:
(1) if x is 0, then y is not 0,
(2) if y is 0, then x is not 0, and
(3) x + y is greater than 0.001 and less than 1.
In the above composition, the +3 valence element x is preferably selected from aluminum, iron, chromium, vanadium, molybdenum, arsenic, antimony, manganese, gallium and boron; the +4 valence element Z is preferably selected from silicon, germanium and titanium; the .+5 valence element Y is preferably selected from phosphorous, arsenic, antimony and vanadium. Most preferably, X is aluminum, Y is phosphorus and Z is silicon.
In the composition above, depending on the values of x and y, the composition can be a cation exchange material with potential use as an acidic catalyst, or it can be an anion exchange material with potential use as a basic catalyst.
The composition of the present invention is prepared by providing a reaction mixture comprising sources of X oxide, Y oxide and Z oxide, water, an organic directing agent B, inorganic cations M and. anions N, the components of said reaction mixture having the following relationship:
(D)a:(M20)b:(X203)c:(Z02)d:(Y205)e:(N)g:(H20)h
where a, b, c, d, e, f, g, and h are numbers satisfying the following relationships:
d/(d+2c+2e) is up to 0.2 (preferably 0.05 to 0.2) a/(d+2c+2e) is 0.2 to 0.4, and preferably the addition relationships: b/(c+d+e) is less than 2, c ^ e g/(c-κl+e) is less than 2, and h/(c+d+e) is from 3 to 150,
The initial pH of the reaction mixture should be 4-6. The mixture is heated with agitation to a temperature of 130 to 155°C and maintained at this temperature until crystals of oxide material are formed.
The pH is controlled during the reaction so that the final pH is 6-7 and the reaction to produce at least 70%, and preferably
at least 80% of the composition of the invention (based on the weight of the total crystalline phase) is normally complete after 4-20 hours. The crystalline product is recovered by separating same from the reaction medium, such as by cooling the whole to room temperature, filtering and washing with water before drying.
In some cases it may be desirable to employ a two-phase reaction mixture, in which at least one of the X, Y and Z oxides is dissolved or dispersed in an organic solvent.
The above reaction mixture composition can be prepared from any suitable materials which supply the appropriate components. Useful sources of +3 valence element, e.g. aluminum, include any known form of oxide or hydroxide, organic or inorganic salt or compound. Useful sources of +4 valence element, e.g. silicon, include, any known form of dioxide or silicic acid, alkoxy- or other compounds of such element. Useful sources of +5 valence element, e.g. phosphorus, include, any known form of phosphorus acids or phosphorus oxides, phosphates and phosphites, and organic derivatives of such element.
The organic solvent is a Cr-C,0 alcohol or any other liquid compound substantially immiscible with water.
The organic directing agent can be an organic mono- or dialkylamine, with alkyl being of 3 or 4 carbon atoms, or an onium compounds having the following formula:
R4M+X~ or (R3M+R'M+R3)X2
wherein R or R 1 is alkyl of from 1 to 20 carbon atoms , or combinations thereof ; M is a tetra coordinate element (e.g . nitrogen, phosphorus , arsenic, antimony or bismuth) ; and X is an anion (e .g. fluoride , chloride , bromide , iodide, hydroxide , acetate , sulfate, carboxylate) . Particularly preferred directing agents include tetraethylammonium hydroxide , tetra propylammonium bromide or most preferably tetrapropylammonium hydroxide and dialkylamines wherein alkyl is butyl or most preferably propyl.
In order to avoid the production of unwanted crystalline phases, the temperature must be carefully controlled within the 130 - 155°C range specified abaove. The preferred temperature within this range depends on the directing agent employed, so that with 5 dipropyla ine the preferred temperature is 135 - 155°C, most preferably about 150°C, whereas with tetrapropylammonium hydroxide the preferred temperature is 130 - 145°C, preferably about 135°C.
In its synthesized form the present composition will also contain occluded organic directing agent and water molecules, 1° entrapped during the synthesis and filling the icroporous voids. However, these can be removed by heating.
The original cations of the as-synthesized present composition can be replaced in accordance with techniques well known in the art, at least in part, by ion exchange with other cations. I5 Preferred replacing cations include metal ions, hydrogen ions, hydrogen precursor, e.g. ammonium, ions and mixtures thereof. Particularly preferred cations are those which render the composition catalytically active or control catalytic activity, especially for hydrocarbon conversion. These include hydrogen, rare
20 earth metal and metals of Groups IA, IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB and VIII of the Periodic Table of the Elements.
A typical ion exchange technique would be to contact the synthetic present composition with a salt of the desired replacing cation or cations. Examples of such salts include the halides, e.g.
25 chlorides, nitrates and sulfates.
The crystalline composition of the present invention can be beneficially thermally treated, either before or after ion exchange. This thermal treatment is performed by heating the composition in an atmosphere such as air, nitrogen, hydrogen, steam, 0 etc., at a temperature of from 300°C to 1100°C, preferably from 350°C to 750°C, for from 1 minute to 20 hours. While subatmospheric or superatmospheric pressures may be used for this thermal treatment, atmospheric pressure is desired for reasons of convenience.
It may be desirable to incorporate the new composition with another material, i.e. a matrix, resistant to the temperatures and other conditions employed in various organic conversion processes. Such materials include active and inactive material and synthetic or naturally occurring zeolites as well as inorganic 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 or gels including mixtures of silica and metal oxides. Catalyst compositions containing the present composition will generally comprise from 1% to 90% by weight of the present composition and from 10% to 99% by weight of the matrix material. More preferably, such catalyst compositions will comprise from 2% to 80% by weight of the present composition and from 20% to 98% by weight of the matrix. Use of a material in conjunction with the new composition, i.e. combined therewith, which is active, tends to alter the conversion and/or selectivity of the overall catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to cont--ol 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 of reaction. These materials may be incorporated into naturally occurring clays, e.g. bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions. Said materials, i.e. clays, oxides, etc., function as binders for the catalyst. It may be desirable to provide a catalyst having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials. These clay binders have been employed normally only for the purpose of improving the crush strength of the overall catalyst. Naturally occurring clays which can be composited with the new crystal include the montmorillonite and kaolin families which include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or
anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the present composition can be composited with a porous matrix material such as aluminum phosphate, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alu ina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia. The relative proportions of finely divided crystalline material and inorganic oxide gel matrix vary widely, with the crystal content ranging from 1 to 90 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of 2 to 80 weight percent of the composite.
Employing a catalytically active form of the present composition as a catalyst component, said catalyst possibly containing additional hydrogenation components, reforming stocks can be reformed employing a temperature of 370°C to 540°C, a pressure of 100 psig to 1000 psig (791 to 6996 kPa), preferably from 200 psig to
700 psig (1480 to 4928 kPa), a liquid hourly space velocity is of 0.1 to 10, preferably 0.5 to 4, and a hydrogen to hydrocarbon mole ratio of 1 to 20, preferably 4 to 12.
A catalyst comprising the present composition can also be used for hydroisomerization of normal paraffins, when provided with a hydrogenation component, e.g. platinum. Such hydroisomerization is carried out at a temperature of 90°C to 375°C, preferably 145°C to 290°C, with a liquid hourly space velocity of 0.01 to 2, preferably 0.25 to 0.50, and with a hydrogen to hydrocarbon mole ratio of 1:1 to 5:1. Additionally, such a catalyst can be used for olefin or aromatic isomerization, employing a temperature of 200°C to 480°C.
Such a catalyst can also be used for reducing the pour point of gas oils. This reaction is carried out at a liquid hourly space velocity of 10 to 30 and at a temperature of 425°C to 595°C.
Other reactions which can be accomplished employing a catalyst comprising the composition of this invention containing a metal, e.g. platinum, include hydrogenation-dehydrogenation reactions and desulfurization reactions, olefin polymerization (oligomerization) and other organic compound conversions, such as the conversion of alcohols (e.g. ethanol) or ethers (e.g. dimethylether) to hydrocarbons, and the alkylation of aromatics (e.g. benzene) in the presence of an alkylating agent (e.g. ethylene).
The invention will now be more particularly described with reference to the Examples and the accompanying drawings, in which:
Figure 1 shows the X-ray diffraction pattern of the as-synthesized Example 1 product;
Figure 2 shows the X-ray diffraction pattern of the calcined Example 1 product; and
Figure 3 shows the X-ray diffraction pattern of the as-synthesized Example 3 product; and
Figure 4 shows the X-ray diffraction pattern of the calcined Example 3 product.
EXAMPLE 1 A two-phase synthesis reaction mixture was prepared with the organic phase comprising lOg Si (OC2H5)4 and 60g 1-hexanol, and the aqueous phase comprising 23g H,P04 (85%), 14g A1203, lOg di-n-propylamine (DPA) and 60g of H20. The reaction mixture as a whole had the following approximate composition:
Si/Si+A1+P = 0.1 DPA/Si+Al+P = 0.2
The reaction mixture had a starting pH of 5.5 and having been stirred without heating for 15 minutes, was heated at 50°C per hour to 150°C and maintained at that temperature for 24 hours while being stirred at 800 rpm until crystals of silicophosphoaluminate formed. The final pH was 7.
The crystalline product was separated from the reaction mixture by filtration, washed with toluene and ether and then dried. A sample of the product was then submitted for X-ray analysis and found to be a crystalline composition exhibiting the diffraction lines shown in Table 2A. The X-ray diffraction pattern of this sample is shown in Figure 1. This product, after calcination at 450°C in nitrogen and air for four hours each, was found to have the X-ray pattern shown in Table 2B and Figure 2.
Table 2A
*dif fraction lines identifying a crystal .framework topology having pore windows formed by 18 tetrahedral members .
**diffraction lines of * plus additiosal intensity contribution from other crystalline phase.
*diffraction lines identifying a crystal framework topology having pore windows formed by 18 tetrahedral members.
**diffraction lines of * plus additional intensity contribution from other crystalline phase.
*** doublet.
Analysis of the X-ray data of the as-synthesized and calcined products showed the the crystalline phase contained in excess of 80% by weight of the crystalline material of the invention having the X-ray lines listed in Tables 1A and IB.
EXAMPLE 2 The process of Example 1 was repeated but with the reaction mixture being heated at 50°C/hour to 130°C, maintained at this temperature for 24 hours , heated to 200°C, and then maintained at this temperature for 24 hours . In this case, although the composition having the X-ray lines listed in Tables 1A and B was present, it constituted less than 70% by weight of the overall crystalline product .
Example 3
A mixture containing 38.3 g of 85% orthophosphoric acid (HτP04) in 50 g water was mixed with 22.97 g hydrated aluminium oxide (Kaiser A1-0- . The mixture was heated to 80°C with stirring for 1/2 hour. To this mixture was added 108.8 g tetrapropylammonium hydroxide (TPAOF 25%). Crystallization in an autoclave was at 135°C at autogenous pressure for 16 hours. The solid product was filtered, washed and dried. Figure 3 shows the X-ray diffraction pattern of the as-synthesized material and Figure 4 shows that of the calcined material (calcined at 538°C in N_ for 2 hours). Tables 3 and 4 show X-ray powder diffraction data of the as-synthesized and calcined samples, respectively.
Analysis of the X-ray information indicated that the crystalline product of this example contained in excess of 90% by weight of a material having the X-ray lines of Tables 1A and IB.
Table 3
Interplanar d-Spacings (A)
16.3 13.4 12.0 11.4
9.3
8.10
6.85
6.15
5 .97
5 .39
4.670
4.496
4.384
4.241
4.143
4.066
4.014
3.946
3.707
3.531
3.431
3.388
3.246
3.104
Table 4
Interplanar d-Spacings (A)
Claims
1. A synthetic crystalline molecular sieve composition comprising at least 70% by weight of a crystalline material having the X-ray diffraction lines in Table 1A by weight of the crystalline phase..
2. The composition of claim 1 wherein said material has the X-ray diffraction lines listed in Table IB.
3. The composition of claim 1 wherein the crystal framework of sad material has the following composition:
OTO2);„y :(Y02)J_χ :(Z02)χ+y wherein X is a +3 valence element, Y is a +5 valence element, Z is a +4 valence element, and x and y are each greater than -1 and less than +1.
4. The composition of claim 4 wherein x and y satisfy the further relationships
(i) if x is 0, then y is not 0,
(ii) if y is 0, then x is not 0, and
(iii) x + y is greater than 0.001 and less than 1.
5. The composition of claim 3 or claim 4 wherein X is aluminum, Y is phosphorus and Z is silicon.
6. A method of producing the composition of claim 3 comprising the step of providing a reaction mixture comprising water, sources of oxides of the elements X, Y and Z, an organic directing agent D, inorganic cations M and anions N is the following molar relationship
(D)a:C^0)b:(X203)c:(Z0£)d:(Y205)e: (Solvent)f:(N) :(F20)h wherein a/(d+2c+2e) is up to 0.2 d/(d+2c+2e) is 0.2 to 0.4
and heating the mixture to a temperature of 130 - 155°C for 4 - 20 hours.
7. The method of claim 6 wherein the mixture obeys the following additional relationships:
a/(d+2c+2e) is 0.05 to 0.2, b/(c+d-*e) is less than 2, c e, g/(c+d+e) is less than 2, and h/(c+d+e) is from 3 to 150,
8. The method of claim 5 or claim 6 wherein the directing ag-.nt is dipropylamine and said temperature is 135 - 155°C.
9. The method of claim 5 or claim 6 wherein the directing agent is a tetrapropylammonium compound and said temperature is 130
- 145°C.
10. The method of claim 5 or claim 6 wherein the initial pH of said mixture is 4 - 6.
11. The method of claim 10 wherein the final pH of the mixture is 6-7.
12. The method of claim 5 or claim 6 wherein the mixture comprises an aqueous phase and an organic phase, at least one of said oxides being dispersed or dissolved in the. organic phase and the mixture being agitated to admix the phases during the heating step.
4550h/0334h
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019890701471A KR900700382A (en) | 1987-12-21 | 1988-12-16 | Crystalline molecular sieve |
AU29240/89A AU614107B2 (en) | 1987-12-21 | 1988-12-16 | Crystalline molecular sieve |
DK150590A DK150590A (en) | 1987-12-21 | 1990-06-20 | SYNTHETIC CRYSTALLINIC MOLECULE SIGT MATERIAL AND PROCEDURE FOR PREPARING THIS |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US136,083 | 1987-12-21 | ||
US07/136,083 US4880611A (en) | 1983-12-19 | 1987-12-21 | Crystalline composition |
US17390288A | 1988-03-28 | 1988-03-28 | |
US173,902 | 1988-03-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1989005775A1 true WO1989005775A1 (en) | 1989-06-29 |
Family
ID=26833979
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1988/004482 WO1989005775A1 (en) | 1987-12-21 | 1988-12-16 | Crystalline molecular sieve |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0393138A4 (en) |
JP (1) | JPH03504372A (en) |
AU (1) | AU2924089A (en) |
CA (1) | CA1329798C (en) |
DK (1) | DK150590A (en) |
NZ (1) | NZ227383A (en) |
WO (1) | WO1989005775A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0406872A2 (en) * | 1989-07-07 | 1991-01-09 | VAW Aluminium AG | Method for the preparation of a large-pored crystalline molecular sieve |
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 |
WO2001025151A1 (en) * | 1999-10-01 | 2001-04-12 | Exxon Chemical Patents, Inc. | Process for the synthesis of silicoaluminophosphate molecular sieves |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1661859A1 (en) * | 2004-11-26 | 2006-05-31 | Total France | Zeolite compositions and preparation and use thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4673559A (en) * | 1983-12-19 | 1987-06-16 | Mobil Oil Corporation | Silicoaluminophosphate crystallization using hydrolysis |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1989001912A1 (en) * | 1987-08-28 | 1989-03-09 | The Dow Chemical Company | Crystalline aluminumphosphate compositions |
-
1988
- 1988-12-16 WO PCT/US1988/004482 patent/WO1989005775A1/en not_active Application Discontinuation
- 1988-12-16 JP JP50121489A patent/JPH03504372A/en active Pending
- 1988-12-16 AU AU29240/89A patent/AU2924089A/en active Granted
- 1988-12-16 EP EP19890901225 patent/EP0393138A4/en not_active Withdrawn
- 1988-12-19 CA CA 586337 patent/CA1329798C/en not_active Expired - Fee Related
- 1988-12-19 NZ NZ22738388A patent/NZ227383A/en unknown
-
1990
- 1990-06-20 DK DK150590A patent/DK150590A/en not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4673559A (en) * | 1983-12-19 | 1987-06-16 | Mobil Oil Corporation | Silicoaluminophosphate crystallization using hydrolysis |
Non-Patent Citations (3)
Title |
---|
See also references of EP0393138A4 * |
Zeitschrift fur Kristallographie, Vol. 136, issued 1972, BAERLOCHER et al. "The Structure of the Synthetic Zeolite (K, Ba)-G,L, (pages 245-254; especially Table 1, page 247). * |
Zeolites, Volume 8, issued September 1988 (Stoneham, Massachusetts), DAVIS et al., "VPI-5: The First Molecular Sieve with Pores Larger than 10 Angstroms", (pages 362-366). * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0406872A2 (en) * | 1989-07-07 | 1991-01-09 | VAW Aluminium AG | Method for the preparation of a large-pored crystalline molecular sieve |
EP0406872A3 (en) * | 1989-07-07 | 1992-01-02 | Vereinigte Aluminium-Werke Aktiengesellschaft | Method for the preparation of a large-pored crystalline molecular sieve |
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 |
WO2001025151A1 (en) * | 1999-10-01 | 2001-04-12 | Exxon Chemical Patents, Inc. | Process for the synthesis of silicoaluminophosphate molecular sieves |
WO2001025150A1 (en) * | 1999-10-01 | 2001-04-12 | Pop, Grigore | Process for the synthesis of silicoaluminophosphate molecular sieves |
US6514899B1 (en) | 1999-10-01 | 2003-02-04 | Exxonmobil Chemical Patents, Inc. | Process for the synthesis of silicoaluminophosphate molecular sieves |
AU777353B2 (en) * | 1999-10-01 | 2004-10-14 | Exxonmobil Chemical Patents Inc | Process for the synthesis of silicoaluminophosphate molecular sieves |
Also Published As
Publication number | Publication date |
---|---|
AU2924089A (en) | 1989-07-19 |
CA1329798C (en) | 1994-05-24 |
DK150590D0 (en) | 1990-06-20 |
DK150590A (en) | 1990-08-21 |
NZ227383A (en) | 1991-05-28 |
EP0393138A4 (en) | 1992-01-02 |
JPH03504372A (en) | 1991-09-26 |
EP0393138A1 (en) | 1990-10-24 |
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