CN102548937A - 使用uzm-35来进行烃的催化裂化的方法 - Google Patents
使用uzm-35来进行烃的催化裂化的方法 Download PDFInfo
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- CN102548937A CN102548937A CN2010800371321A CN201080037132A CN102548937A CN 102548937 A CN102548937 A CN 102548937A CN 2010800371321 A CN2010800371321 A CN 2010800371321A CN 201080037132 A CN201080037132 A CN 201080037132A CN 102548937 A CN102548937 A CN 102548937A
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- CN
- China
- Prior art keywords
- uzm
- zeolite
- weight
- ammonium
- catalytic cracking
- Prior art date
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- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 30
- 230000008569 process Effects 0.000 title claims abstract description 27
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 20
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 150000001336 alkenes Chemical class 0.000 claims abstract description 18
- 239000011734 sodium Substances 0.000 claims abstract description 11
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011591 potassium Substances 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 6
- 150000001768 cations Chemical class 0.000 claims abstract description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 239000010457 zeolite Substances 0.000 claims description 82
- 229910021536 Zeolite Inorganic materials 0.000 claims description 69
- 239000002994 raw material Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 10
- JPOUMZSEEKDHFQ-UHFFFAOYSA-N O(O)O.C[N+](CCC)(CCC)C Chemical compound O(O)O.C[N+](CCC)(CCC)C JPOUMZSEEKDHFQ-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- XBMRWQWMMIYMLY-UHFFFAOYSA-N CN(C)C.C(CCC)N Chemical compound CN(C)C.C(CCC)N XBMRWQWMMIYMLY-UHFFFAOYSA-N 0.000 claims description 4
- WQHRRUZRGXLCGL-UHFFFAOYSA-N dimethyl(dipropyl)azanium Chemical compound CCC[N+](C)(C)CCC WQHRRUZRGXLCGL-UHFFFAOYSA-N 0.000 claims description 4
- GJZAMOYERKVOGF-UHFFFAOYSA-N dimethyl-di(propan-2-yl)azanium Chemical compound CC(C)[N+](C)(C)C(C)C GJZAMOYERKVOGF-UHFFFAOYSA-N 0.000 claims description 4
- SDZQEZNDOPDYPP-UHFFFAOYSA-N n,n-dimethylmethanamine;propan-1-amine Chemical compound CCCN.CN(C)C SDZQEZNDOPDYPP-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- VFOJFWOVDZGATC-UHFFFAOYSA-N methyl(tripropyl)azanium Chemical compound CCC[N+](C)(CCC)CCC VFOJFWOVDZGATC-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims 2
- 125000002091 cationic group Chemical group 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 30
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 16
- -1 dimethyldipropylammonium cation Chemical class 0.000 abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 description 33
- 239000000463 material Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000003502 gasoline Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 4
- 238000003991 Rietveld refinement Methods 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 239000003915 liquefied petroleum gas Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 3
- 229960001231 choline Drugs 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- MXTMXRYBYWOAGX-UHFFFAOYSA-N dimethyl(diphenyl)azanium Chemical compound C=1C=CC=CC=1[N+](C)(C)C1=CC=CC=C1 MXTMXRYBYWOAGX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 101100008638 Caenorhabditis elegans daf-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KSGUUTWSWMLVHG-UHFFFAOYSA-N N.OOO Chemical compound N.OOO KSGUUTWSWMLVHG-UHFFFAOYSA-N 0.000 description 1
- DPWHVPKWZJRFMZ-UHFFFAOYSA-N O(O)O.C(C)[N+](C)(C)C Chemical compound O(O)O.C(C)[N+](C)(C)C DPWHVPKWZJRFMZ-UHFFFAOYSA-N 0.000 description 1
- JYGZZNYPDYJBOO-UHFFFAOYSA-N O(O)O.C(C)[N+](C)(C)CC Chemical compound O(O)O.C(C)[N+](C)(C)CC JYGZZNYPDYJBOO-UHFFFAOYSA-N 0.000 description 1
- LVHFFCVSWIOHPR-UHFFFAOYSA-N O(O)O.C(C)[N+](CC)(CC)CC Chemical compound O(O)O.C(C)[N+](CC)(CC)CC LVHFFCVSWIOHPR-UHFFFAOYSA-N 0.000 description 1
- BUXZQTOWKVNISA-UHFFFAOYSA-N O(O)O.C[N+](C(C)C)(C(C)C)C Chemical compound O(O)O.C[N+](C(C)C)(C(C)C)C BUXZQTOWKVNISA-UHFFFAOYSA-N 0.000 description 1
- ZQSVNPGQCFYFIC-UHFFFAOYSA-N OOO.C(CC)[N+](CCC)(CCC)CCC Chemical compound OOO.C(CC)[N+](CCC)(CCC)CCC ZQSVNPGQCFYFIC-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- WRMFBHHNOHZECA-UHFFFAOYSA-N butan-2-olate Chemical compound CCC(C)[O-] WRMFBHHNOHZECA-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 101150091051 cit-1 gene Proteins 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- ZJHQDSMOYNLVLX-UHFFFAOYSA-N diethyl(dimethyl)azanium Chemical compound CC[N+](C)(C)CC ZJHQDSMOYNLVLX-UHFFFAOYSA-N 0.000 description 1
- KHBDINVATPZDSQ-UHFFFAOYSA-M dimethyl(dipropyl)azanium;bromide Chemical compound [Br-].CCC[N+](C)(C)CCC KHBDINVATPZDSQ-UHFFFAOYSA-M 0.000 description 1
- LMPJXBZCHHYCKS-UHFFFAOYSA-M dimethyl-di(propan-2-yl)azanium;bromide Chemical compound [Br-].CC(C)[N+](C)(C)C(C)C LMPJXBZCHHYCKS-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- YOMFVLRTMZWACQ-UHFFFAOYSA-N ethyltrimethylammonium Chemical compound CC[N+](C)(C)C YOMFVLRTMZWACQ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 1
- 229910000373 gallium sulfate Inorganic materials 0.000 description 1
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 1
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
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Abstract
通过uzm-35家族的结晶铝硅酸盐沸石组合物来对催化裂化工艺方法,诸如流化催化裂化,石脑油裂化,和烯烃裂化进行催化,所述uzm-35组合物具有如下经验组成:
Description
发明背景
本发明涉及沸石UZM-35在催化裂化有机化合物的方法中的应用。沸石UZM-35可存在于催化裂化催化剂中,作为唯一沸石组分,或者可以在UZM-35组合物中与其他沸石,诸如MFI沸石和ERI沸石一起。沸石UZM-35或UZM-35组合物可以作为合成形式(未改性的沸石)或作为改性形式的沸石存在于催化剂中。该催化剂可具有数个形式之一,包括,例如,固体可流体化(solid fluidizable)的催化剂,球形油滴法催化剂(sphericaloil-dropped)或挤出的催化剂(extruded catalyst)。
沸石是结晶铝硅酸盐组合物,多孔且由共角(corner sharing)的AlO2和SiO2四面体构成。天然形成或合成制备的多种沸石用于各类工业方法过程中。合成沸石通过采用适宜的Si、Al源物质以及结构导向剂如碱金属、碱土金属、胺或有机铵阳离子经水热合成来制备。结构导向剂残留在沸石孔中并大大地决定着最终形成的特定结构。这些物质平衡着和铝有关的骨架电荷,并且还可充当空间填充物。沸石的特征在于具有均匀尺寸的开孔,具有显著的离子交换容量,并且能够可逆地解吸分散遍布晶体内部空隙的吸收相而不显著置换任何构成永久沸石晶体结构的原子。拓扑沸石结构在国际沸石协会结构委员会(International Zeolite Association StructureCommission)维护的沸石骨架类型目录(Atlas of Zeolite Framework Types)中有所描述,其网址是http://www.iza-structure.org/databases/。沸石可用作烃转化反应的催化剂,该转化可在外表面或者孔内内表面上发生。
在炼油厂的数个领域中都用到了催化裂化工艺。流化催化裂化(FCC)将重质原料转化为较轻的产物,包括柴油,汽油和轻质烯烃。FCC传统上被用于重质原料的转化,诸如VGO(真空瓦斯油)转化为汽油和柴油,但是近来已经被延展到丙烯的共产生(co-production)。该方法典型地使用12元环和/或10元环沸石的至少一种,诸如FAU或MFI,从而以高选择性催化重质原料到汽油和/或丙烯的转化。石脑油裂化(naphtha cracking)已经被深入研究,使用12元环或10元环沸石以高选择性来转化石脑油原料为丙烯。烯烃裂化使用10元环沸石催化剂,诸如MFI和MEL,以高选择性来转化烯属原料诸如丁烯或戊烯。在所有这些催化裂化工艺中,需要新的催化剂,其具有高的总体原料转化率和良好的丙烯选择性。
尤其有利的是,商业可用的催化剂在同一三维结构中含有12元环和10元环。在氢氧化物介质中合成的,并具有容易获得的结构导向剂的铝硅酸盐结构,可典型地具有商业实用性。在三维结构中同时含有12元环和10元环的沸石属于CON、DFO、IWR、IWW和MSE结构类型。在US5,512,267和J.Am.Chem.Soc.1995,117,3766-79中描述了作为硼硅酸盐形式的CIT-1的合成,其为CON结构类型的沸石。在合成后,可进行后续步骤来允许Al取代为B。沸石SSZ-26和SSZ-33,其为CON结构类型,也在US4,910,006和US4,963,337中分别进行描述。SSZ-33也被描述为硼硅酸盐。CON结构类型的全部三成员使用非常复杂,难以合成结构导向剂,其使得商业化应用很困难。DFO结构类型的已知成员是DAF-1,其在Chem.Commun.1993,633-35和在Chem.Mater.1999,11,158-63中描述为磷铝酸盐。来自IWR和IWW结构类型的沸石仅仅在含氢氟酸的合成路线中进行合成,使得商业化应用很困难。
一个MSE结构类型的特殊沸石,标记为MCM-68,由Calabro等人在1999(US6,049,018)进行公开。该专利描述了MCM-68由双阳离子导向剂(directing agent),N,N,N′,N′-四烷基双环[2.2.2]辛-7-烯-2R,3S:5R,6S-二吡咯烷鎓双阳离子,和N,N,N′,N′-四烷基双环[2.2.2]辛烷-2R,3S:5R,6S-二吡咯烷鎓双阳离子进行的合成。已发现MCM-68具有至少一个通道系统,其中各通道由四面体配位的原子的12元环来定义,和至少两个另外独立通道系统,其中各通道由四面体配位的原子的10元环来定义,其中唯一10元环通道的数量两倍于12元环的数量。
本申请人已经成功地制备出新一族的材料,标记为UZM-35。材料的拓扑结构与MCM-68观察到的那些相似。该材料通过利用简单的市购的结构导向剂,诸如二甲基二丙基铵氢氧化物,与少量K+和Na+相呼应,使用对于沸石合成的电荷密度不匹配(Charge Density Mismatch Approach)途径来进行制备(US7,578,993)。
由于其特殊的孔隙几何学和骨架Si/Al比率,该UZM-35家族的材料能够提供并且维持在催化裂化反应时的高转化率和对丙烯的高选择性。UZM-35材料在四面体骨架中含有大量Al,其Si/Al的摩尔比从2到12。已知的是,在骨架中的Al含量对应于在催化裂化工艺方法中的高活性。
由于UZM-35的独特结构,由UZM-35制得的催化剂能够显示出正庚烷的高转化率以及对烯烃的良好选择性。在正庚烷的裂化中,UZM-35在500℃转化了大于70%的正庚烷,对丙烯的高选择性为34%,对轻质烷(C1,C2,C3)的选择性仅有12%。比较起来,对于同样量的沸石,DHCD-4-CB(MFI型催化剂)转化了84%的正庚烷原料,对丙烯的选择性仅仅为30%。另外,DHCD-4在这些条件下,对轻质烷的选择性为15%。
在通过催化裂化来转化C4-烯烃到丙烯时,UZM-35催化剂也有效。相比于参比的MFI催化剂,在相似的轻质烯烃产出,以及等价的转化率条件下,UZM-35具有远远更高的转化率。对于参比的MFI,在580℃,7psig,13.5WHSV下,实现了55重量%的转化率,对丙烯的选择率为65重量%。对于UZM-35,在520℃,7psig,40WHSV下,实现了52重量%转化率,对丙烯的选择率为63.5重量%。UZM-35在远远较不苛刻的条件下,对于大致相似的轻质烯烃产率下,对运行给出了有利的性能。
发明概述
本发明涉及了使用名为UZM-35的铝硅酸盐沸石催化剂,来进行烃催化裂化的方法。该方法包括了,在催化裂化条件下,用UZM-35接触烃,来获得催化裂化的烃类产物。
UZM-35是微孔晶体沸石组合物,其具有至少AlO2和SiO2四面体单元的三维框架,并具有以下经验组成的合成形式和无水形式表示的经验组成:
Mm +R+ rAl1-xExSiyOz
其中M表示钾和钠交换性阳离子的组合,″m″是M对(Al+E)的摩尔比,为0.05到3,R是带单电荷的的有机铵阳离子,其选自如下组成的组,二甲基二丙基铵(DMDPA+)、二甲基二异丙基铵(DMDIP+),胆碱,乙基三甲基铵(ETMA+),二乙基二甲基铵(DEDMA+),三甲基丙基铵,三甲基丁基铵,二甲基二乙醇基铵,四乙基铵(TEA+),四丙基铵(TPA+),甲基三丙基铵,和它们的混合物,″r″是R对(Al+E)的摩尔比,其值为0.25到2.0,E是选自如下组成的组的元素,镓,铁,硼和它们的混合物,″x″是E的摩尔分数,其值为0到1.0,″y″是Si对(Al+E)的摩尔比,其值为大于2到12,″z″是O对(Al+E)的摩尔比,其值由如下方程式决定:
z=(m+r+3+4·y)/2
以及,其特征在于其x射线衍射图具有至少在表A列出的d间距和强度
表A
并且在一实施方案中,在高达大于400℃时,其是热稳定的,在另一实施方案中,在高达大于600℃时,其是热稳定的。当使用在J.Appl.Cryst.(1969)2,65-71)中描述的Rietveld精细化方法时,x射线衍射图具有至少在表A’列出的d间距和强度
表A’
如上所述的晶体微孔沸石组合物可通过如下方式进行合成,形成含有反应性源物质的M,R,Al,Si和任选的E的反应混合物,并且在150℃到200℃,或165℃到185℃的温度下加热反应混合物,其时间足够形成沸石组合物,该反应混合物具有以氧化物摩尔比来表示的如下组成:
aM2O:bR2/pO:1-cAl2O3:cE2O3:dSiO2:eH2O
其中″a″具有0.05到1.25的值,″b″具有1.5到40的值,″p″是R的加权平均价态,其值为1到2,″c″具有0到1.0的值,″d″具有4到40的值,″e″具有25到4000的值。
发明详述
本申请人已经制备了名为UZM-35组合物的铝硅酸盐沸石组合物,其主要成分具有涉及MSE的拓扑沸石结构,其在国际沸石协会结构委员会(International Zeolite Association Structure Commission)维护的沸石骨架 类型目录(Atlas of Zeolite Framework Tvpes)中有所描述,网址是http://www.iza-structure.org/databases/。正如USAN12/241,302详细所述的,在许多特性中,UZM-35与MCM-68不同。该微孔晶体沸石组合物,UZM-35,具有基于如下经验式表示的合成形式并且无水基的经验组成:
Mm +R+ rAl1-xExSiyOz
其中M表示钾和钠交换性阳离子的组合。R是带单电荷的的有机铵阳离子,其实例包括但不限于二甲基二丙基铵阳离子(DMDPA+)、二甲基二异丙基铵(DMDIP+),胆碱[(CH3)3N(CH2)2OH]+,ETMA+,DEDMA+,三甲基丙基铵,三甲基丁基铵,二甲基二乙醇基铵,甲基三丙基铵,TEA+,四TPA+,和它们的混合物,″r″是R对(Al+E)的摩尔比,其值为0.25到2.0,同时″m″是M对(Al+E)的摩尔比,为0.05到3。″y″是硅对(Al+E)的摩尔比,其值为2到30。E是四面体配位的元素,其在骨架中,并选自如下组成的组的元素,镓,铁,和硼。″x″是E的摩尔分数,其值为0到1.0,同时″z″是O对(Al+E)的摩尔比,其值由如下方程式决定:
z=(m·n+r+3+4·y)/2
其中,M是仅一金属,然后加权平均价态是该一金属的价态,即+1或者+2。然而,当存在超过一个M金属时,总量为:
并且,加权平均价态“n”通过如下公式给出:
微孔晶体沸石组合物,UZM-35,通过如下方式制备,将反应混合物进行水热结晶,所述反应混合物通过将M,R,铝,硅和任选的E进行组合来制备。铝的来源包括但不限于铝醇盐,沉淀氧化铝,铝金属,铝盐和氧化铝溶胶。铝醇盐的特定实例包括,但不限于原仲丁醇铝(aluminumortho sec-butoxide)和原异丙醇铝氧化物(aluminum ortho isopropoxide)。二氧化硅的来源包括但不限于正硅酸乙酯,胶态氧化硅,沉淀二氧化硅和碱金属硅酸盐。E元素的来源包括但不限于碱金属硼酸盐,硼酸,沉淀氧氢氧化镓(gallium oxyhydroxide),硫酸镓,硫酸铁,和氯化铁。M金属,钾和钠的来源物质,包括各碱金属的盐酸盐,硝酸盐,乙酸盐,和氢氧化物。R是有机铵阳离子,其选自由如下组成的组,二甲基二丙基铵离子、胆碱,ETMA,DEDMA,TEA,TPA,三甲基丙基铵,三甲基丁基铵,二甲基二乙醇基铵,和它们的混合物,并该源物质包括氢氧化物,氯化物,溴化物,碘化物和氟化物化合物。特定例子包括,但不限于二甲基二丙基铵氢氧化物、二甲基二丙基铵氯化物,二甲基二丙基铵溴化物,二甲基二异丙基铵氢氧化物,二甲基二异丙基铵氯化物,二甲基二异丙基铵溴化物,乙基三甲基铵氢氧化物,二乙基二甲基铵氢氧化物,四乙基铵氢氧化物,四丙基铵氢氧化物,和四丙基铵氯化物。
注意,在合成期间,该金属M是+1价态,特定地是钾和钠。然而,在备选实施方案中,组合物可经历另外的离子交换步骤,以在合成之后,提供了具有一种或者多种具有+2价态的金属M的材料。
含有想要组分的反应性源物质的反应混合物可以氧化物摩尔比率,通过如下结构式来进行描述:
aM2O:bR2/pO:1-cAl2O3:cE2O3:dSiO2:eH2O
其中″a″具有0.05到1.25的值,″b″具有1.5到40的值,″c″具有0到1.0的值,″d″具有4到40的值,″e″具有25到4000的值,″p″是R的加权平均价态,其值为1到2。如果使用了醇盐,优选的是,包括蒸馏或蒸发步骤来除去醇水解产物。反应混合物现在在150℃到200℃,165℃到185℃,或者170℃到180℃下在密封反应容器中,在自生压力下反应1天到3周,优选5天到12天。在结晶完成之后,通过诸如过滤或离心手段来将固体产物从非均匀混合物来进行分离,然后用去离子水进行洗涤,并在环境温度到高达100℃下在空气中干燥。应当指出,UZM-35晶种可任选地加入反应混合物中,以便加速沸石的形成。
优选的制造UZM-35的合成方法使用了电荷密度不匹配概念,其公开在US7,578,993和Studies in Surface Science and Catalysis,(2004),Vol.154A,364-372。公开在US7,578,993的方法使用了季铵氢氧化物来溶解铝硅酸盐物质,同时结晶诱导剂,诸如碱和碱土金属和更高度带电的有机铵阳离子常常被引入到分离步骤中。一旦一些UZM-35晶种已使用该方法生成,晶种可在UZM-35的单一步骤合成中使用,其使用,例如,二甲基二丙基铵氢氧化物和碱阳离子的组合。通过利用可市购的二甲基二丙基铵氢氧化物来制备UZM-35,相比于之前使用的结构导向剂(N,N,N′,N′-四烷基双环[2.2.2]辛-7-烯-2R,3S:5R,6S-二吡咯烷鎓双阳离子,和N,N,N′,N′-四烷基双环[2.2.2]辛烷-2R,3S:5R,6S-二吡咯烷鎓双阳离子)来制备具有MSE拓扑结构的铝硅酸盐,提供了很大的经济优势。另外,二甲基二丙基铵氢氧化物可以作为氢氧化物或氯化物和其他便宜的有机铵氢氧化物一致使用电荷密度不匹配概念来使用,从而甚至进一步降低成本。
该UZM-35铝硅酸盐沸石组合物,其从上述方法中获得,其特征在于,x射线衍射图中具有至少表A所示的d间距和相对强度。
表A
正如实施例中详细所示的,UZM-35材料,在高达至少400℃时,在另一实施方案中,高达600℃时,其是热稳定和催化稳定的。合成形式的UZM-35组合物包含MSE拓扑结构沸石,MFI拓扑结构沸石和ERI拓扑结构沸石。典型地,MSE沸石在组合物的量为约55重量%到约75重量%,或约55重量%到约90重量%。MFI沸石的量为组合物约20重量%到约35重量%,或约10重量%到约35重量%,ERI沸石的量为组合物的约3重量%到约9重量%,或约3重量%到约10重量%。当然,三种沸石的总量,在没有任何其他杂质时,总计达到组合物的100重量%。当然,三种沸石的总量,在没有任何其他杂质时,总计达到组合物的100重量%。当使用J.Appl.Cryst.(1969)2,65-71描述的Rietveld精细化方法时,x射线衍射图具有至少表A′所示的d间距和强度:
表A’
UZM-35材料的一个优点是,其可用作催化裂化催化剂,而不需要从合成形式的材料中除去钾。换句话说,不需要为了使催化裂化催化剂进行活化而去除钾。处于催化活性状态的该催化剂,可含有相对于氧化铝的摩尔比率低于0.90的钾。
合成后,该UZM-35材料将在其孔隙中含有一些可交换的或电荷平衡的阳离子。这些可交换的阳离子可与其它阳离子进行交换,或在有机阳离子的情况下,它们可以通过在控制条件下进行加热来去除。因为该UZM-35组合物包括大孔隙沸石,还可能的是,通过离子交换来直接除去一些有机阳离子。该UZM-35组合物可以通过许多方式进行改性,来进行定制以便用于特定应用场合。改性包括煅烧,离子交换,气蒸(steaming),各种酸萃取,铵六氟硅酸盐处理,或者它们的任何结合,正如在US6,776,975B1中对UZM-4M所叙述的,其在此全文引入作为参考。改性的性能包括孔隙度,吸附,Si/Al摩尔比,酸性,热稳定性,等等。
上述的该UZM-35组合物或其改性物,在各种烃催化裂化工艺中被用作催化剂或催化剂载体。该催化剂可含有从30或40到80重量%的UZM-35组合物。烃类的催化裂化是本领域公知的工艺方法,包括例如,流化催化裂化(FCC),石脑油裂化,和烯烃裂化。裂化方法是用于将复杂的有机分子,诸如重质烃类断裂成为更简单的分子的工艺方法,其通过典型地在催化剂的存在下来断开前体中的碳-碳键实现。催化裂化工艺方法包括酸催化剂的存在(通常是固体酸,诸如二氧化硅-氧化铝和沸石),其促进了键的破坏,产生了较小分子量的烯烃和链烷烃。另外地,发生了分子内和分子间的氢转移或氢化物转移以及诸如低聚和芳构化的反应。裂化速率和最终产品性能取决于工艺方法进行时的条件,诸如温度,压力,催化剂和原料进行接触的时间量和所用的任何催化剂的性质。
流化催化裂化(FCC)是一种广泛使用的催化裂化工艺方法。该方法典型地使用粉状催化剂,其中颗粒悬浮在上升流动的原料烃类中来形成流化床。沸石基催化剂通常被用作是复合催化剂,其含有沸石,二氧化硅-氧化铝,氧化铝和其它粘合剂。在代表性的工艺方法中,裂化发生在升管(riser)中,其是垂直的或上斜的(upward sloped)。
预加热的原料(例如,真空瓦斯油)可以通过原料喷嘴来喷进入升管基部,在此原料在400-800℃下接触热的流化催化剂。该原料在与催化剂接触时蒸发,并发生裂化,将高分子量油转化为更轻的组分,其包括液化石油气(LPG),汽油,和馏出物。该催化剂-原料混合物在短时间内(数秒)通过升管向上流动,然后混合物在旋风分离器(cyclones)中被分离。由此与催化剂分离的烃类被导入分馏器中,来分离成LPG,汽油,柴油,煤油,喷气燃料,和其他可能的级分。
在通过升管的同时,该裂化催化剂被减活,因为该方法伴随着在催化剂颗粒上沉积焦炭的形成。所以沾污的催化剂从裂化的烃类蒸气中被分离,进一步用蒸汽处理来除去留在催化剂孔隙中的烃类。该催化剂然后被导入到再生器中,在再生器中焦炭从催化剂颗粒表面被烧掉,由此还原了催化剂活性,并提供了下一个反应周期所必须的热量。裂化工艺方法是吸热的。再生的催化剂然后被用于新的循环周期。用于催化裂化工艺方法,诸如FCC的新催化剂因此应该能够再生。该UZM-35组合物,在一个实施方案中,就再生而言是稳定的。
催化裂化工艺方法通过UZM-35组合物进行,其使用原料,诸如瓦斯油,重石脑油,循环油,脱沥青原油残留物,费-托蜡,疏松石蜡(slack wax),上述的氢化处理产物,和它们的组合,其中汽油是典型的想要的产物。400-800℃的温度条件,0到688kPag(0到100psig)的压力条件和从0.1秒到1小时的接触时间是合适的。450-700℃的温度条件,0到344kPag(0到50psig)的压力条件和从0.1秒到数分钟的接触时间是通常优选的。该优选的条件基于要裂化的烃类原料和想要的裂化产物来决定。
石脑油裂化方法优选是通过UZM-35组合物进行,使用石脑油原料,诸如,但不限于,直馏石脑油,焦化石脑油,减粘裂化石脑油(Visbreakernaphtha),FCC石脑油,和催化聚合石脑油(Cat Polynaphtha),其被催化裂化成为轻质烯烃,诸如乙烯和丙烯。该石脑油与UZM-35组合物催化剂在,例如,流化催化裂化(FCC)型反应器中进行接触。可选择任意类型的反应器以将催化剂与石脑油原料流进行密切混合。对本领域技术人员而言,该类型的反应器是熟知的。在本发明中可使用的流化燃料反应器在US6,183,699中有所描述,其在此全文引入作为参考。
备选地,反应器类型,诸如具有连续催化剂再生的移动床反应器,或者通过压力摆动或者温度摆动而具有周期性催化剂再生的固定床反应器,均可用来将烃类原料与UZM-35沸石催化剂进行接触。用于催化裂化工艺方法,诸如石脑油裂化的新催化剂因此应该能够再生。该UZM-35组合物,在一个实施方案中,就再生而言是稳定的。
该石脑油裂化反应可以在400℃到700℃之间的温度下进行。裂化工艺方法可以使用0到688kPag(0到100psig)的压力条件和从0.1秒到1小时,优选0.1秒到0.1小时的接触时间,来进行。假设所有其他工艺变量等同时,在较低温度下使用较长的接触时间,同样在较高温度下使用较短的时间。
烯烃裂化法优选通过UZM-35组合物进行,使用原料诸如混合烯烃料流,其包括C4或C5到C10烯烃,其中乙烯,丙烯,和丁烯是主要想要的产品。在一些应用场合中,丁烯也可再循环来进行裂化。烯烃裂化反应器的操作在400℃到650℃,并且优选在500℃到600℃之间进行。在工作期间,烯烃裂化反应器的压力为0kPa到344kPa之间,优选的工作压力为10kPa到200kPa之间,对于烯烃分压而言。烯烃裂化工艺方法的接触时间为从0.1秒到1小时。
C4或C5到C10烯烃原料从UZM-35催化剂床上通过,来裂化烯烃成为更小的分子。裂化工艺方法在催化剂上生成一些结焦,随着时间,由于催化剂孔隙被焦炭堵塞,催化剂活性被减低。该催化剂可以通过氧化焦炭,并以气体方式除去来进行再生,所述气体主要包括N2,H2O,CO和CO2。在反应器中的催化剂可周期性地再生,因此该工艺方法可以在频繁的基础上在多个反应器之间进行摆动。备选地,反应器类型,诸如具有催化剂连续再生的移动或流化床反应器,可以用来将烃类原料与UZM-35组合物进行接触。用于催化裂化工艺方法,诸如烯烃裂化的新催化剂因此应该能够再生。该UZM-35组合物,在一个实施方案中,就再生而言是稳定的。
另外的沸石可以与UZM-35组合物进行结合。例如,可将一种或多种FAU或MFI结构类型的沸石与UZM-35组合物进行复合。UZM-35对一种或者多种FAU或MFI结构类型的沸石的重量比可以是0.01到50。在其他应用场合,UZM-35对一种或者多种FAU或MFI结构类型的沸石的重量比可以是0.01到1。
反应区排放液通常地从催化剂床移出,进行部分冷凝和蒸气-液态分离,然后进行分级来回收其各种组分。氢,和如果想要的话,一些或所有的未转化的较重材料,被再循环到反应器中。备选地,二级的料流可以与正通过第二反应器的未转化材料一起使用。
下列实施例用于说明本发明,而不是对本发明通用宽泛范围的过度限制,本发明的范围在附加的权利要求书中进行界定。
本发明的UZM-35沸石组合物的结构通过X射线分析进行测定。在下列实施例中的X射线图样使用标准x射线粉末衍射法来获得。辐射源是在45kV和35ma时进行操作的高强度x射线管。铜K-alpha辐射的衍射图样是通过适当的计算机技术来获得。平面压缩粉末样品在2°到56°(2θ)之间被连续扫描。以埃单位表示的晶面间距(d)从表示为θ的衍射峰位置来获得,其中θ是从数字化数据观察得到的Bragg角。从减去噪音之后的衍射峰的积分面积来测定强度,″Io″是最强线或峰的强度,″I″是其它的各峰的强度。
本领域技术人员将理解的是,参数2θ的测定受到人员和机械误差的影响,二者联合可对各报导的2θ值赋予±0.4°的不确定度。当然,该不确定性也在d-间距的报道值中体现出来,其是从2θ值计算而来。该不精确度在本领域中是常见的,不足以消除该结晶物质彼此之间以及与现有技术的组合物之间的差异性。在一些报道的x射线图案中,d-间距的相对强度通过符号vs,s,m和w来表示,其分别表示非常强(verystrong),强(strong),中等(medium),和弱(weak)。就100×I/Io而言,上述符号被定义为:
w=0-15;m=15-60:s=60-80和vs=80-100
实施例7和8是合成实施例,其使用了被称为Rietveld精细化方法的X射线衍射技术,描述在J.Appl.Cryst.(1969)2,65-71。
在特定情况下,合成产品的纯度可以根据其x射线粉末衍射图案来进行估计。因此,例如,如果样品是纯的,其仅意味着样品的x射线图案不具有可归因于晶体杂质的线,但不意味着不存在非晶体材料。
为了更完全地解释本发明,给出下列实施例。应该明了的是,实施例仅仅用于解释说明的目的,而不意味着对本发明宽范围的限制,本发明的范围由附加的权利要求进行界定。
实施例1
首先将27.17g的氢氧化铝(27.78重量%的Al)和1053.58g二甲基二丙基铵氢氧化物(18.8重量%溶液)进行混合,同时强烈搅拌,来制备铝硅酸盐反应溶液。在充分混合以后,加入505.96g LudoxTM AS-40(40重量%SiO2)。用高速机械搅拌器对反应混合物另外均化1小时,密封在特氟隆瓶子中,并放入100℃的烘箱中过夜。分析显示该铝硅酸盐溶液含有6.16重量%的Si和0.67重量%的Al(Si/Al摩尔比率为8.83)。
连续搅拌上述铝硅酸盐溶液的1200g部分。将复合材料水溶液,其含有溶解在150g蒸馏水中的28.56g的KOH和3.6g的NaOH,逐滴加入该铝硅酸盐溶液中。在加入结束之后,均化得到的反应混合物1小时,转移到2000ml的Parr不锈钢高压釜中,加热至175℃,并保持在此温度216小时。通过离心作用来回收固体产品,用去离子水清洗,并在100℃下干燥。
通过离心作用来回收固体产物,用去离子水清洗,并在95℃下干燥。通过XRD来确定产物为UZM-35。观察该产品得到的代表性的衍射线显示在表1中。产物组成通过元素分析来测定,其由如下摩尔比的物质组成:Si/Al=7.92,Na/Al=0.1,K/Al=0.48。
表1
实施例2
将实施例1的UZM-35在540℃煅烧10小时,在氮气下,然后在空气中。然后对UZM-35进行铵离子交换,来将Na或K阳离子兑换成NH4。通过将500mL的1M的NH4NHO3溶液与40g UZM-35在80℃下进行接触,并搅拌1小时,过滤并清洗,来对UZM-35进行铵离子交换。重复该程序三次。
实施例3
然后将实施例2的UZM-35在550℃,在空气中煅烧2小时,通过损失氨来将NH4 +转化为H+。
实施例4
备选地,首先进行铵交换,接着进行煅烧来除去模板,并交换Na+或K+成NH4 +。通过将500mL的1M的NH4NHO3溶液与30g UZM-35在80℃下进行接触,并搅拌1小时,来对实施例1的UZM-35进行铵离子交换。将样品在540℃下煅烧10小时,在氮气中,然后在空气中。通过将500mL的1M的NH4NHO3溶液与22g UZM-35在80℃下进行接触,并搅拌1小时,来进行第二次铵离子交换。
对比实施例5
获得H-MFI沸石的样品,其与AlPO4以66/34结合比。该材料的SiO2/Al2O3摩尔比是38。
对比实施例6
获得H-MFI沸石的样品,其与SiO2以80/20结合。在使用之前,该催化剂已经锻烧和汽蒸处理过。该材料的SiO2/Al2O3摩尔比是500。
在用于催化作用之前,UZM-35的H+形式被压缩,并过筛至20-40目。对于正庚烷裂化测验,将250mg的沸石载入反应器,用正庚烷饱和的N2料流以125mL/min在大气压力下与催化剂进行接触。对于被测试为结合催化剂的催化剂,使用250mg的沸石。也就是说,对于由100%沸石组成的催化剂,使用250mg的催化剂,但是对于含有50%沸石的催化剂,使用500mg的催化剂。该正庚烷裂化测验的结果显示在表2。
表2
正庚烷裂化测验后,将UZM-35催化剂从反应器中卸下,并发现其从白色变成黑色,表明了碳的存在。废催化剂样品的XRD分析显示,该UZM-35结构在催化作用条件下是稳定的。UZM-35可在550℃,在空气中煅烧3小时来进行再生。XRD分析表明,UZM-35仍然是完整的。
对于丁烯裂化测验,将5g的过筛的催化剂载入反应器,并将60/40异丁烷/异丁烯混合物与催化剂床,在7psig,27到40WHSV,520到580℃下进行接触。该丁烯裂化测验的结果显示在表3。
表3
丁烯裂化测验后,将UZM-35催化剂从反应器中卸下,并发现其从白色变成黑色,表明了C的存在。对这些废催化剂样品进行XRD分析,显示,该UZM-35结构在催化作用条件下是稳定的。UZM-35可在550℃,在空气中煅烧3小时来进行再生。XRD分析表明,UZM-35仍然是完整的。
实施例7
首先将86.33g的氢氧化铝(26.79重量%的Al)和1437.67g二甲基二丙基铵氢氧化物(40.66重量%溶液)进行混合,同时强烈搅拌,来制备铝硅酸盐反应溶液。在充分混合以后,加入1366.88g LudoxTM AS-40(SiO2,40重量%)。用高速机械搅拌器对反应混合物均化20分钟,将铝硅酸盐胶体溶液持续搅拌,逐滴加入含有溶解在808.7g H2O的83.04g的KOH和17.38g的NaOH的水溶液,到该铝硅酸盐溶液中。在加入结束之后,均化得到的反应混合物1/2小时,转移到(3)2000ml的Parr不锈钢高压釜中,加热至175℃,并保持在此温度9天。通过离心作用来回收固体产品,用去离子水清洗,并在100℃下干燥。
该反应获得的产物通过X射线衍射(Rietveld精细化方法,其描述在J.Appl.Cryst.(1969)2,65-71)确定为以下的UZM-35组合物:72.1重量%MSE型沸石,对于a,点阵参数(lattice parameter)为18.372埃,对于c为20.285埃;24.1重量%MFI沸石,对于a,点阵参数为20.101埃,对于b为19.862埃,对于c为13.402埃,和3.7重量%ERI沸石,对于a,点阵参数为13.222埃,对于c为14.900埃。化学分析给出产物组成为,Si/Al的摩尔比=8.9。BET表面积被测定为408m2/g,微孔体积是0.197cc/g。对于该产品,观察到的代表性衍射线显示在表4中。
表4
将样品在600℃煅烧10小时,在氮气下,然后在空气中。煅烧得到的产物通过X射线衍射(Rietveld精细化方法,其描述在J.Appl.Cryst.(1969)2,65-71)确定为如下的混合物:64.4重量%MSE型沸石,其对于a,点阵参数为18.371埃,对于c为20.235埃;30.7重量%MFI沸石,其对于a,点阵参数为20.048埃,对于b为19.880埃,对于c为13.403埃,和3.7重量%ERI沸石,对于a,点阵参数为13.071埃,对于c为15.238埃。对于该产品,观察到的代表性衍射线显示在表5中。
表5
实施例8
首先将29.01g的氢氧化铝(26.79重量%的Al)和483.08g二甲基二丙基铵氢氧化物(40.66重量%溶液)进行混合,同时强烈搅拌,来制备铝硅酸盐反应溶液。在充分混合以后,加入461.58g LudoxTMAS-40(SiO2,40重量%)。用高速机械搅拌器对反应混合物均化20分钟,将铝硅酸盐胶体溶液持续搅拌,逐滴加入含有溶解在269.98g H2O的27.90g的KOH和3.46g的NaOH的水溶液,到该铝硅酸盐溶液中。在加入结束之后,均化得到的反应混合物1/2小时,转移到2000ml的Parr不锈钢高压釜中,加热至175℃,并保持在此温度10天。通过过滤来回收固体产品,用去离子水清洗,并在100℃下干燥。
该反应获得的产物通过X射线衍射(Rietveld精细化方法,其描述在J.Appl.Cryst.(1969)2,65-71)确定为以下的UZM-35组合物:66.3重量%MSE型沸石,对于a,点阵参数为18.369埃,对于c为20.284埃;25.5重量%MFI沸石,对于a,点阵参数为20.136埃,对于b为19.976埃,对于c为13.443埃,和8.2重量%ERI沸石,对于a,点阵参数为13.152埃,对于c为15.107埃。化学分析给出产物组成为,Si/Al的摩尔比=7.65,N/Al=0.38,K/Al=0.68,Na/Al=0.03。BET表面积被测定为404m2/g,微孔体积是0.188cc/g。对于该产品,观察到的代表性衍射线显示在表6中。
表6
将样品在600℃煅烧10小时,在氮气下,然后在空气中。煅烧得到的产物通过X射线衍射(Rietveld精细化方法,其描述在J.Appl.Cryst.(1969)2,65-71)确定为以下的UZM-35组合物:61.9重量%MSE型沸石,其对于a,点阵参数为18.401埃,对于c为20.280埃;30.8重量%MFI沸石,其对于a,点阵参数为20.114埃,对于b为19.919埃,对于c为13.432埃,和7.3重量%ERI沸石,对于a,点阵参数为13.189埃,对于c为15.174埃。
对于该产品,观察到的代表性衍射线显示在表7中。
表7
Claims (10)
1.一种催化裂化的方法,其包括,将烃类原料与催化剂在催化裂化条件下进行接触,并生产裂化的产品,其中催化剂包含UZM-35微孔结晶沸石组合物,其中UZM-35具有至少AlO2和SiO2四面体单元的三维框架结构,并具有合成形式和基于无水表示的经验组成,其经验组成式为:
Mm +R+ rAl1-xExSiyOz
其中M表示钾和钠交换性阳离子的组合,″m″是M对(Al+E)的摩尔比,为0.05到3,R是带单电荷的二甲基二丙基铵阳离子,″r″是R对(Al+E)的摩尔比,其值为0.25到2.0,E是选自如下组成的组的元素:镓,铁,硼和它们的混合物,″x″是E的摩尔分数,其值为0到1.0,″y″是Si对(Al+E)的摩尔比,其值为大于2到12,″z″是O对(Al+E)的摩尔比,其值由如下方程式决定:
z=(m+r+3+4·y)/2
以及,其特征在于其x射线衍射图具有至少在表A’列出的d间距和强度
表A’
并且在高达至少400℃时,其是热稳定的。
2.权利要求1的方法,其中原料的初始沸点大于200℃。
3.权利要求2的方法,其中原料选自由如下组成的组:瓦斯油,重石脑油,循环油,脱沥青原油残留物,费-托蜡,疏松石蜡,氢化处理的瓦斯油,氢化处理的重石脑油,氢化处理的循环油,氢化处理的脱沥青原油残留物,氢化处理的费-托蜡,氢化处理的疏松石蜡和它们的组合。
4.权利要求2的方法,其中所述催化裂化条件包括400-800℃的温度,0到688kPag(0到100psig)的压力和从0.1秒到1小时的接触时间。
5.权利要求1的方法,其中UZM-35组合物包含MSE结构沸石、MFI结构沸石和ERI结构沸石。
6.权利要求1的方法,其中UZM-35组合物包含从55重量%到75重量%的MSE沸石,从20重量%到35重量%的MFI沸石,和从3重量%到9重量%的ERI沸石。
7.权利要求1的方法,其中R是二甲基二丙基铵氢氧化物和至少一种带单电荷的有机铵阳离子的组合,所述有机铵阳离子选自如下组成的组:TEA,TPA,ETMA,DEDMA,三甲基丙基铵,二甲基二异丙基铵离子,三甲基丁基铵,二甲基二乙醇基铵,和甲基三丙基铵。
8.权利要求1的方法,其中原料包含沸程为25℃到225℃的石脑油。
9.权利要求8的方法,其中所述催化裂化条件包括400-700℃的温度,0到688kPag(0到100psig)的压力和从0.1秒到1小时的接触时间。
10.权利要求1的方法,其中烃类原料包含C4到C10的烯烃,裂化产物包含乙烯、丙烯和丁烯。
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CN106413889A (zh) * | 2014-06-04 | 2017-02-15 | 雪佛龙美国公司 | 分子筛ssz‑99 |
CN106457232A (zh) * | 2014-06-04 | 2017-02-22 | 雪佛龙美国公司 | 制备分子筛ssz‑99的方法 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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US8247631B2 (en) * | 2010-06-21 | 2012-08-21 | Uop Llc | Process for catalytic cracking of hydrocarbons using UZM-35 |
EP2457890A1 (en) | 2010-11-29 | 2012-05-30 | Cognis IP Management GmbH | Biocide compositions comprising alkoxylation products of isoamyl alcohol derivatives |
US8895790B2 (en) | 2013-02-12 | 2014-11-25 | Saudi Basic Industries Corporation | Conversion of plastics to olefin and aromatic products |
US9447332B2 (en) | 2013-02-12 | 2016-09-20 | Saudi Basic Industries Corporation | Conversion of plastics to olefin and aromatic products using temperature control |
US9428695B2 (en) | 2013-02-12 | 2016-08-30 | Saudi Basic Industries Corporation | Conversion of plastics to olefin and aromatic products with product recycle |
SG11201701991VA (en) | 2014-10-14 | 2017-04-27 | Exxonmobil Res & Eng Co | Removal of occluded alkali metal cations from mse-framework type molecular sieves |
KR101795404B1 (ko) * | 2016-05-18 | 2017-11-08 | 현대자동차 주식회사 | 촉매 및 촉매의 제조 방법 |
JP7467475B2 (ja) | 2018-12-26 | 2024-04-15 | ピーティーティー グローバル ケミカル パブリック カンパニー リミテッド | C4-c7炭化水素から軽質オレフィンを製造するための触媒 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1484615A (zh) * | 2000-11-03 | 2004-03-24 | �Ʒ� | 结晶状硅铝酸盐沸石组合物:uzm-4以及使用该组合物的方法 |
WO2005042149A1 (en) * | 2003-10-31 | 2005-05-12 | Uop Llc | A process for preparing crystalline aluminosilicate compositions using charge density matching |
CN1642857A (zh) * | 2002-02-12 | 2005-07-20 | 环球油品公司 | 结晶硅铝酸盐沸石组合物:uzm-9 |
CN102171146A (zh) * | 2008-09-30 | 2011-08-31 | 环球油品公司 | Uzm-35硅铝酸盐沸石、制备方法和使用uzm-35的方法 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4310440A (en) | 1980-07-07 | 1982-01-12 | Union Carbide Corporation | Crystalline metallophosphate compositions |
US4440871A (en) | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
US4735929A (en) | 1985-09-03 | 1988-04-05 | Uop Inc. | Catalytic composition for the isomerization of paraffinic hydrocarbons |
US4910006A (en) | 1988-03-23 | 1990-03-20 | Chevron Research Company | Zeolite SSZ-26 |
US4963337A (en) | 1989-07-07 | 1990-10-16 | Chevron Research Company | Zeolite SSZ-33 |
WO1995007859A1 (en) | 1993-09-15 | 1995-03-23 | Davis Mark E | Zeolite cit-1 |
US6049018A (en) | 1999-01-21 | 2000-04-11 | Mobil Corporation | Synthetic porous crystalline MCM-68, its synthesis and use |
US6310265B1 (en) | 1999-11-01 | 2001-10-30 | Exxonmobil Chemical Patents Inc. | Isomerization of paraffins |
US7198711B1 (en) | 2000-01-21 | 2007-04-03 | Exxonmobil Research And Engineering Company | Catalytic cracking processing using an MCM-68 catalyst |
US6506953B1 (en) | 2000-01-24 | 2003-01-14 | Exxonmobil Oil Corporation | Hydroalkylation of aromatic hydrocarbons |
US6776975B2 (en) | 2002-05-09 | 2004-08-17 | Uop Llc | Crystalline aluminosilicate zeolitic composition: UZM-4M |
US6756030B1 (en) * | 2003-03-21 | 2004-06-29 | Uop Llc | Crystalline aluminosilicate zeolitic composition: UZM-8 |
MXPA06012271A (es) * | 2004-04-20 | 2007-01-26 | Uop Llc | Composiciones zeoliticas de aluminosilicatos cristalinos uzm-8 y uzm-8hs y procesos que utilizan estas composiciones. |
US8562941B2 (en) | 2005-12-20 | 2013-10-22 | Exxonmobil Research And Engineering Company | Perturbed synthesis of materials |
-
2009
- 2009-06-22 US US12/489,026 patent/US7981273B2/en active Active
-
2010
- 2010-06-21 EP EP10797549.2A patent/EP2445857A4/en not_active Withdrawn
- 2010-06-21 CN CN2010800371321A patent/CN102548937A/zh active Pending
- 2010-06-21 WO PCT/US2010/039370 patent/WO2011005483A2/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1484615A (zh) * | 2000-11-03 | 2004-03-24 | �Ʒ� | 结晶状硅铝酸盐沸石组合物:uzm-4以及使用该组合物的方法 |
CN1642857A (zh) * | 2002-02-12 | 2005-07-20 | 环球油品公司 | 结晶硅铝酸盐沸石组合物:uzm-9 |
WO2005042149A1 (en) * | 2003-10-31 | 2005-05-12 | Uop Llc | A process for preparing crystalline aluminosilicate compositions using charge density matching |
CN102171146A (zh) * | 2008-09-30 | 2011-08-31 | 环球油品公司 | Uzm-35硅铝酸盐沸石、制备方法和使用uzm-35的方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106413889A (zh) * | 2014-06-04 | 2017-02-15 | 雪佛龙美国公司 | 分子筛ssz‑99 |
CN106457232A (zh) * | 2014-06-04 | 2017-02-22 | 雪佛龙美国公司 | 制备分子筛ssz‑99的方法 |
CN106413889B (zh) * | 2014-06-04 | 2018-09-18 | 雪佛龙美国公司 | 分子筛ssz-99 |
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