CN110300623A - 具有混合氧化铝的fcc催化剂添加剂 - Google Patents
具有混合氧化铝的fcc催化剂添加剂 Download PDFInfo
- Publication number
- CN110300623A CN110300623A CN201880012482.9A CN201880012482A CN110300623A CN 110300623 A CN110300623 A CN 110300623A CN 201880012482 A CN201880012482 A CN 201880012482A CN 110300623 A CN110300623 A CN 110300623A
- Authority
- CN
- China
- Prior art keywords
- additive
- zeolite
- aluminium oxide
- alumina
- small
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 239000000654 additive Substances 0.000 title claims abstract description 63
- 230000000996 additive effect Effects 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 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 59
- 239000010457 zeolite Substances 0.000 claims abstract description 58
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 14
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000004411 aluminium Substances 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 239000004927 clay Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 26
- 239000011574 phosphorus Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 238000005336 cracking Methods 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- 235000011007 phosphoric acid Nutrition 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910001679 gibbsite Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000004231 fluid catalytic cracking Methods 0.000 abstract description 22
- 239000007800 oxidant agent Substances 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 3
- -1 Halogen ion Chemical class 0.000 description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 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 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910001680 bayerite Inorganic materials 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- NHEULQMXMXIOJY-UHFFFAOYSA-N Cl[PH2]=O Chemical compound Cl[PH2]=O NHEULQMXMXIOJY-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-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
- 241000282326 Felis catus Species 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960000892 attapulgite Drugs 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- OOSPDKSZPPFOBR-UHFFFAOYSA-N butyl dihydrogen phosphite Chemical compound CCCCOP(O)O OOSPDKSZPPFOBR-UHFFFAOYSA-N 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- ZUKLAAHCPUBQLQ-UHFFFAOYSA-N diethylphosphinous acid Chemical compound CCP(O)CC ZUKLAAHCPUBQLQ-UHFFFAOYSA-N 0.000 description 1
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229960000443 hydrochloric acid Drugs 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UTEFBSAVJNEPTR-RGEXLXHISA-N loprazolam Chemical compound C1CN(C)CCN1\C=C/1C(=O)N2C3=CC=C([N+]([O-])=O)C=C3C(C=3C(=CC=CC=3)Cl)=NCC2=N\1 UTEFBSAVJNEPTR-RGEXLXHISA-N 0.000 description 1
- 229960003019 loprazolam Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- RYIOLWQRQXDECZ-UHFFFAOYSA-N phosphinous acid Chemical compound PO RYIOLWQRQXDECZ-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- PZHNNJXWQYFUTD-UHFFFAOYSA-N phosphorus triiodide Chemical compound IP(I)I PZHNNJXWQYFUTD-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7034—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- 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
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- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/28—Phosphorising
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- 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
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Abstract
提供了一种流体催化裂化催化剂添加剂组合物及其制备方法。该催化剂添加剂组合物包含约35wt%至约80wt%、优选约40wt%至约70wt%的沸石;约0wt%至约10wt%、优选约2wt%至约10wt%的二氧化硅;约10.5wt%至20wt%的氧化铝和约7wt%至20wt%、优选约11wt%至约18wt%的P2O5,以及可在0与50wt%之间的余量粘土。氧化铝通常衍生自多于一种的源,例如至少无定形或小微晶尺寸的拟薄水铝石氧化铝,然后是大微晶尺寸的氧化铝或其他反应性氧化铝。
Description
技术领域
本发明涉及具有混合氧化铝的流体催化裂化(FCC)材料。更具体地,本发明涉及基于沸石的FCC添加剂及其制备方法。
背景技术
将重质烃原料转化为较轻产物(例如汽油和馏出物范围馏分)的最优选方法之一是流体催化裂化(FCC)。然而,越来越需要提高来自催化裂化方法的产物构成中低级烯烃、LPG的产率和其他轻质烯烃产率(C2-C4烃)。在FCC实践中,有两种方法提高轻质烯烃选择性。第一种方法是增加反应温度。这将增加热裂化的贡献,导致更轻产物的形成增加。例如,在所谓的DCC(深度催化裂化)方法中,使用特定类型的FCC方法、更高的温度和增加的蒸汽量。然而,热裂化不是非常有选择性的,并且在“湿气”(其包含H2和C1-C4产物)中产生大量具有相对较小价值的产物,例如氢气、甲烷、乙烷和乙烯。湿气压缩常常限制炼油厂的操作。
第二种方法是添加烯烃选择性的含沸石的添加剂,例如含ZSM-5的添加剂。常规添加剂通常含有磷活化的ZSM-5,其选择性地将初级裂化产物(例如汽油烯烃)转化为C3和C4烯烃。已知用磷改进活性或选择性以提高ZSM-5的效力。例如,EP-A-511 013描述了用磷处理ZSM-5以提高丙烯选择性。此外,美国专利号5,472,594描述了一种用于用含有沸石Y的催化剂组合物和包含含磷中孔沸石如ZSM-5的添加剂将烃进料转化为含有改进产率的C4/C5烯烃的产物的方法。而且,Mobil的WO 98/41595描述了一种用于使用催化剂组合物催化裂化烃原料以产生提高C3至C5烯烃产率的方法,该催化剂组合物包含大孔分子筛如沸石Y和包含与含有沸石Y的碱催化剂共混的含磷ZSM-5的添加剂。同样的内容描述于美国专利号5,456,821中。WO 94/13754描述了使用含有大孔分子筛的催化剂组合物和含有特定ZSM-5的添加剂的相同方法,该ZSM-5任选含有1.5-5.5wt%的元素磷。另外,美国专利号5,521,133描述了通过在喷雾干燥之前用磷酸注入ZSM-5和高岭土浆料来制备ZSM-5添加剂。
沸石是烃转化中最广泛使用的催化材料之一。它被广泛用作催化裂化器中的催化剂和/或添加剂或掺入裂化催化剂中。在美国专利号3,758,403中已经报道了使用由大孔径结晶沸石(孔径大于7埃单位)与ZSM-5型沸石混合构成的裂化催化剂来提高辛烷值。当含有10%REY的常规催化剂与在1.5%至10%范围内的ZSM-5分子筛一起添加时,汽油辛烷值和低级烯烃的产率增加。然而,已发现随着ZSM-5分子筛量增加,效力降低。使用含有ZSM-5分子筛的添加剂具有相同的效果。
为了增加轻质烯烃的产量和提高对丙烯的选择性,已经尝试增加催化剂体系中沸石如ZSM-5的量。这可以通过增加添加剂中沸石的量或增加与基础FCC催化剂共混的添加剂的量来完成。两种方法都有其缺点。增加添加剂的共混物是以碱催化剂的量为代价并且减少了裂化。已知添加剂中增加的沸石晶体会引起添加剂的某些物理属性的问题。特别地,随着沸石晶体的量增加,粘合效果降低,并且磨损量增加。
增加添加剂中沸石含量的一个实例是在U.S.6,916,757中。‘757专利的发明被描述为具有包含约30%至约85%沸石和包含大于9wt%至约24wt%磷(测量为P2O5)的粘合剂体系组分的添加剂,基于总添加剂的重量,添加的氧化铝的量为总添加剂重量的约5wt%至约10wt%;所述添加剂还具有至少0.2至约1.9的磷与总氧化铝的摩尔比。添加的氧化铝定义为分别添加到起始组分浆料中和分散在催化剂基质中的氧化铝。教导了添加的氧化铝的量低于10%,并且据说这些实例“说明了包含约10%或更少添加的氧化铝的催化剂的优点”。
另一个现有技术实例是美国专利号7,375,048。‘048发明被描述为催化剂,其包含(a)至少约30wt%的中等孔径沸石,(b)约3-15wt%的磷,测量为P2O5,(c)约15至45wt.%的高岭土,以及(d)具有小于50m2/g的BET表面积的除高岭土以外的非反应性金属组分,其中所述非反应性金属组分是α-氧化铝。总体上,该专利描述了非反应性氧化铝组分的量为在3-25wt%,更通常约4-10wt%的范围内。‘048专利还教导了任选地添加反应性氧化铝组分。该组分的量可以为2-20%,但通常为4-8%。反应性或非反应性的氧化铝的总重量为在至少5wt.%的范围内并且通常将在约8-25wt.%范围内。‘048专利进一步发现,已发现添加的非反应性和反应性氧化铝形式的氧化铝的量为大于10%的量是最有用的,包括约12-20wt%的量。
因此,需要一种具有可接受物理特性的高沸石FCC添加剂,其允许添加剂以恒定或改进的水平表现。
发明内容
本发明涉及一种催化材料,该催化材料特别旨在用于裂化方法,在特定催化剂组合物上裂化烃进料以产生比进料烃更低分子量的转化产物烃化合物,例如包含高丙烯馏分和增加的LPG的产物。
典型的FCC添加剂程序如下。将氧化铝和/或二氧化硅粘合剂与所需量的沸石浆料、粘土和磷酸混合。将该混合物送至喷雾干燥器中以制备最终催化剂。为了性能和良好的物理特性,主要是FCC添加剂的ABD和耐磨性,将氧化铝和/或二氧化硅粘合剂添加到催化剂混合物中。氧化铝粘合剂可以是使用单质子酸(如HNO3、HCl、甲酸)机械地或化学地分散或溶解的无定形的薄水铝石、三水铝石、三羟铝石、氧化铝溶胶或拟薄水铝石氧化铝溶胶或其他合适的反应性氧化铝(粒径<3000nm),或溶解于单质子酸中的任何其他铝源或任选地与其他酸(一个实例是H3PO4)产生溶胶型材料。二氧化硅粘合剂可以是呈合适分散形式的二氧化硅源,包括二氧化硅水溶胶、硅胶、二氧化硅溶胶和硅酸。
然而,本发明是基于制造添加剂,其具有两种或更多种反应性氧化铝与磷酸的组合(例如,>10.5wt%的总氧化铝添加到混合物中)。通常,至少一种氧化铝是无定形或小微晶尺寸的氧化铝,并且另一种是大微晶尺寸的薄水铝石型氧化铝或具有除薄水铝石之外的结构的其他反应型氧化铝,例如三水铝石或三羟铝石。氧化铝用任何合适的酸,通过已知的机械手段或通过化学反应而分散或胶溶至粒径<3000nm,或者可以自分散至粒径<3000nm。贯穿本披露内容使用的微晶尺寸应理解为平均微晶尺寸。
根据本发明,提供了一种基于沸石的耐水热FCC催化剂添加剂,其包含:约35wt%至约80wt%的沸石;约0wt%至约10wt%的二氧化硅;约10.5wt%至20wt%的氧化铝和约7wt%至20wt%的P2O5,以及可在0至50wt%之间的余量粘土。使用本领域技术人员的一般常识,各种组分的总量可以为了性能而在以上陈述的范围内最大化。
在本发明的还另一方面,提供了一种用于制备基于沸石的FCC催化剂添加剂的方法,该方法选择性地改进了丙烯的产率。本发明的方法还旨在提供一种FCC添加剂催化剂,其能够提供并维持高丙烯产率持续延长的时间。
从包括所附权利要求的以下详细说明中,本发明的这些和还有其他实施例、优点和特征将变得更加明显。
具体实施方式
除非另有说明,否则本文所用的重量百分比(__%)是指定形式的物质的干基重量百分比,基于其中指定物质或物质形式为成分或组分的产品的总干基重。还应该进一步理解,当在本文中以某种方式描述步骤或组分或元素是优选的时,它们在本披露的初始日期是优选的,并且此种或这些优选当然可以根据给定的情况或者现有技术的未来发展而变化。
本发明的催化剂添加剂通常通过以下方法制备:
(a)将氧化铝和水(或其他合适的水溶液)投料到罐中以形成氧化铝浆料;
(b)化学或机械地分散或胶溶氧化铝,如果需要,至粒径<3000nm;
(c)向氧化铝浆料中投料余量的其他成分,包括沸石源、二氧化硅源、磷源、粘土和任选的额外的氧化铝源;
(d)将浆料送至喷雾干燥器;
(e)收集喷雾干燥的催化剂粉末,并且这是最终的添加剂;
(f)任选地,最终产物可以煅烧,例如在约250℃与约700℃的温度下。
为了本发明的目的,步骤(a)和(c)中提及的反应性氧化铝通常是至少无定形或小微晶尺寸的拟薄水铝石氧化铝,并且然后是大微晶尺寸的氧化铝或其他反应性氧化铝。在本发明中添加的氧化铝是多于一种氧化铝源的混合物。当与磷源混合时,通常认为氧化铝是反应性的。
第一潜在的氧化铝源是鉴定为无定形或小微晶尺寸的拟薄水铝石氧化铝或“小微晶氧化铝”(“SCA”)的氧化铝。这些小微晶氧化铝典型地具有通常小于约10nm的微晶尺寸。小微晶尺寸氧化铝的实例包括拟薄水铝石或氧化铝溶胶,例如聚合氯化铝和非水合硝酸铝。
第二氧化铝源是鉴定为“大微晶氧化铝”(“LCA”)或具有除薄水铝石之外的结构的其他反应性氧化铝的氧化铝。大微晶氧化铝典型地具有通常大于约10nm、并且优选大于约15nm的微晶尺寸。优选的微晶尺寸范围为约25nm或更大。合适的大微晶氧化铝的实例包括薄水铝石源。除了上述LCA之外,第二氧化铝源可以是非薄水铝石源,但仍然与磷是反应性的,例如三水铝石和三羟铝石。
步骤(a)和/或(c)中添加的氧化铝的总量通常为在最终干燥添加剂的约10.5wt%至约20.0wt%的范围内,以Al2O3计算,并且优选在约11.5wt%与约15wt%之间。该氧化铝含量与氧化铝可以在其他组分例如沸石或粘土中测量到的氧化铝分开,并且是源自在这些步骤中添加的氧化铝。优选使用两种或更多种氧化铝源的混合物。优选一种源具有比另一种更低的微晶尺寸。在一个实施例中,较低微晶尺寸的氧化铝的总量通常在2.5wt%至约15wt%的范围内。并且较大微晶尺寸的氧化铝的量通常将为约0wt%至约10wt%。氧化铝的总量保持与上述相同,通常在约10.5wt%至约20.0wt%的范围内。
在上述步骤(b)期间,如果需要,添加酸以分散或胶溶氧化铝。合适的酸包括甲酸、硝酸、次膦酸、乙酸、盐酸、甲磺酸、甲烷磺酸或其他已知的分散酸。氧化铝也可以通过任何已知的物理或机械手段分散,或者可以是自分散的。可替代地,可以添加酸以产生溶胶型材料。
在上述步骤(c)期间,可以使用任何合适的含磷化合物,即具有能够与氢离子反应的共价或离子成分的任何含磷化合物,例如磷酸及其盐,如磷酸二氢铵和磷酸氢二铵、连二磷酸铵、正磷酸铵、正磷酸二氢铵、正磷酸氢铵、磷酸三铵、膦和亚磷酸盐。合适的含磷化合物包括由以下所代表的基团的衍生物:PX3、RPX2、R2PX、R1P、R3P═O、RPO2、RPO(OX)2、PO(OX)3、R2P(O)OX、RP(OX)2、ROP(OX)2、和(RO)2POP(OR)2,其中R是烷基或苯基,并且X是氢、R或卤离子。这些化合物包括伯RPH2、仲R2PH和叔R3P膦,如丁基膦;叔膦氧化物R3PO,如三丁基膦;伯RP(O)(OX)2和仲R2P(O)OX膦酸,如苯膦酸;膦酸酯,如膦酸二乙酯(RO)2P(O)H、二烷基次膦酸酯(RO)P(O)R2;次亚膦酸R2POX,如二乙基次亚膦酸,伯(RO)P(OX)2、仲(RO)2POX和叔(RO)3P亚磷酸酯;及其酯,如单丙酯、烷基二烷基次亚膦酸酯(RO)P2和二烷基亚膦酸酯(RO)2PR。亚磷酸酯的实例包括亚磷酸三甲酯、亚磷酸三乙酯、亚磷酸二异丙酯、亚磷酸丁酯;和焦亚磷酸酯,如四焦亚磷酸酯。所提及的化合物中的烷基含有1-4个碳原子。其他合适的含磷化合物包括卤化磷,如三氯化磷、三溴化磷和三碘化磷,二氯磷酸的烷基酯(alkylphosphorodichloridite)(RO)PCl2,一氯磷酸的二烷基酯(dialkylphosphorochloridite)(RO)2PCl,烷基氯化膦酸(alkyl phosphonochloridate)(RO)(R)P(O)Cl和二烷基氯化膦(dialkyl phosphinochloridate)R2P(O)Cl。
在步骤(c)期间添加的磷的量优选为约11wt%至约18wt%的P2O5,但在催化剂上为在约7wt%至约20wt%的P2O5范围内,以干重计。
在步骤(c)期间添加的沸石是典型的烯烃选择性沸石,其定义为具有高于10、优选高于15的二氧化硅/氧化铝比率以及最高达12个环的沸石。通常,添加到混合物中的沸石量为约35wt%至约80wt%,优选约40wt%至约70wt%。
合适的烯烃选择性沸石的实例是MFI型沸石,MEL型沸石如ZSM-11,MTW型沸石如ZSM-12,MWW型沸石如MCM-22、MCM-36、MCM-49、MCM-56,BEA型沸石,如β沸石、ZSM-35和ZSM-22。MFI型沸石是优选的。MFI型沸石如ATLAS OF ZEOLITE STRUCTURE TYPES[沸石结构类型集],W.M.Meier和D.H.Olson,第3修订版(1992),Butterworth-Heinemann中所定义,并且包括ZSM-5、ST-5、ZSM-8、ZSM-11、硅沸石、LZ-105、LZ-222、LZ-223、LZ-241、LZ-269、L2-242、AMS-1B、AZ-1、BOR-C、硼硅沸石、Encilite、FZ-1、NU-4、NU-5、T5-1、TSZ、TSZ-III、TZ01、TZ、USC-4、USI-108、ZBH、ZB-11、ZBM-30、ZKQ-1B、ZMQ-TB。应注意,在本说明书的上下文中,NL9301333中描述的ZRP沸石不被认为是MFI型沸石。
此外,在步骤(c)期间,通常添加在约0wt%至约15wt%范围内的二氧化硅粘合剂。为了最佳的粘合和性能,更优选将约2wt%至约10wt%的二氧化硅粘合剂添加到浆料中。适当分散形式的二氧化硅源包括二氧化硅水溶胶、硅胶、二氧化硅溶胶和硅酸。优选的二氧化硅源是二氧化硅颗粒的水性胶体分散体。适用于本发明的二氧化硅溶胶是源自离子交换方法或具有在约10至约2000埃范围内的基本均匀粒径的其他手段的那些中的任一种。
添加剂的余量是粘土,例如高岭土、膨润土或偏高岭土,或其他填料。这将包括任何合适的非沸石无机氧化物材料以及其他粘土,如多水高岭土或凹凸棒石。
如先前所指出的,所得催化剂添加剂通常包含约35wt%至约80wt%、优选约40wt%至约70wt%的沸石;约0wt%至约10wt%、优选约2wt%至约10wt%的二氧化硅;约10.5wt%至20wt%的氧化铝和约7wt%至20wt%、优选约11wt%至约18wt%的P2O5,以及可在0与50wt%之间的余量粘土。氧化铝通常衍生自多于一种的源,例如至少无定形或小微晶尺寸的拟薄水铝石氧化铝,并且然后是大微晶尺寸的氧化铝或其他反应性氧化铝,如上所述。
根据本发明的组合物可以与烃进料同时与一种或多种催化剂一起添加FCC单元中,或者在添加烃进料和一种或多种催化剂之后添加。在一个实施例中,将根据本发明的组合物与一种或多种FCC催化剂组合。所述催化剂组合物可适合用于烃原料的催化裂化,并且在保持底部物转化率的同时,在生产轻质烯烃中具有高效率。即使当DCC方法中使用比通常更低的温度时,该催化剂组合物也可用于所谓的DCC方法。该材料也可用于HSFCC和石脑油转化方法。
实施例
在以下非限制性实施例中说明本发明,提供这些实施例是为了表示的目的,并且不应解释为限制本发明的范围。
在任何实验室测试之前,催化剂必须失活以模拟炼油厂单元中的催化剂,这通常用蒸汽完成。这些样品通过用Ni/V的循环失活(由在蒸汽存在下的裂化、汽提和再生步骤组成)或在较高温度下用100%蒸汽来失活,这些是工业上接受的FCC催化剂失活方法。失活步骤是本领域已知的,并且对催化活性是必需的。在商业FCC设置中,失活在催化剂引入后不久发生,并且不需要作为单独的步骤进行。流体微活性测试或流化床模拟测试(FST)或高级裂化评估(ACE)是本领域已知且通常被接受的用于确定催化剂的FCC裂化活性的测试。在ACE中,用一系列四种催化剂与进料比(CTO)进行测试,这些催化剂与进料比通过改变注入反应器的进料的质量而获得,同时对于所有运行使用相同量的催化剂。测试设备模拟具有已知量和组成特征的烃原料的已知量的裂化。这种小型测试单元是单程单元,并且大致如ASTM 5154-10中那样操作。对于测试添加剂,在性能测试之前将其与FCC催化剂以一定浓度混合,以模拟商业用途。对于以下实施例,添加剂以5%共混物共混。使用改进的ASTM程序测量磨损指数(AI)。
以下实施例使用典型的VGO原油。可以使用其他进料并且进料性质确实影响LPG以及特别是丙烯的绝对产率。
背景对比例。为了比较本发明的累积效果和益处,使用两种目前可用的商业产品作为对比例。第一种产品是40%沸石添加剂,并且另一种是50%沸石添加剂。当进行上述测试时,与单独的Ecat相比,40%添加剂(A-40)在74%转化率下显示出0.70ABD、0.35AI和3.2wt%的丙烯产率增加。当进行上述测试时,与单独的Ecat相比,50%添加剂(A-50)在74%转化率下显示出0.52AI和约4wt%的丙烯产率增加。与下面的实施例相比,显示出由于通过使用如本文所述的本发明添加更多的沸石,可以保持相似的物理性质和更好的性能。
实施例1.使用本文所述的方法制备六种添加剂样品。将样品中沸石的量保持在50%,以比较本发明相对于当前现有技术的益处。在该实施例和以下实施例中使用的LCA具有约25-30nm的微晶尺寸。在该实施例和以下实施例中使用的SCA具有约4-5nm的微晶尺寸。六种样品具有以下配方:
表1:
*与A-50相比,在测试误差内的当量
然后对这六种添加剂进行性能测试,以根据上述测试程序确定物理特性。在该实施例中,显示出可以使用双源氧化铝制备具有足够性能和更好物理特性的添加剂。从以上结果可以看出,在相同的沸石含量下,可以制备具有改善的磨损和类似的(如果不是改进的)丙烯产量的催化剂。
实施例2.在这组实施例中,沸石总量增加至60%。因此,预期丙烯产量会增加,但也会有一些磨损损失。然而,如结果表明,可以在60%沸石催化剂中保持强的物理特性。实施例2利用与实施例1相同的氧化铝源。
表2:
实施例3.在该实施例中,检查了SCA与LCA的比率以及不同的P2O5含量。该组中的所有样品含有约5wt%的二氧化硅溶胶。此数据显示在样品中可以具有相同百分比的SCA,但添加的P2O5量将对性能具有影响。比较实施例3-3和3-5,发现由于优化的P2O5与SCA比率,对于50%ZSM-5添加剂的丙烯产率在实施例3-5中高了1wt%。此外,看起来P2O5与SCA的重量比优选高于1.7。实施例3利用与实施例1相同的氧化铝源。
表3:
实施例4.在该实施例中,检查了使用三水铝石作为大晶体氧化铝源。首先将三水铝矿在其引入之前研磨至优选低于2微米。当与具有50%ZSM-5的商业添加剂相比时,当SCA和LCA的平衡与总P2O5含量匹配时,以下结果示出更好的物理特性和相同的性能。在该实施例和以下实施例中使用的LCA具有约235nm的微晶尺寸。在该实施例和以下实施例中使用的SCA具有约4-5nm的微晶尺寸。
表4:
如本文所使用的,修饰本发明的或本发明的方法中使用的组合物的成分的量的术语“约”是指例如通过以下方式可能发生的以数字表示的数量上的变化:在真实世界中用于制作浓缩物或使用溶液的典型测量和液体处理程序;这些程序中的非故意的错误;制造组合物或进行这些方法所使用的成分的制造、来源或纯度的差异等。术语“约”还涵盖由于产生自特定起始混合物的组合物的不同平衡条件而不同的量。无论是否由术语“约”修饰,权利要求包括这些量的等同量。
除非另有明确说明,否则如果并且如在本文中使用的冠词“一个/种(a/an)”并非旨在并且不应被解释为将说明书或权利要求限制于该冠词所指的单个元素。相反,除非文本另有明确说明,否则如果并且如在本文中使用的冠词“一个/种(a/an)”旨在涵盖一个或多个这样的元素。本发明在其实践中易受相当大的变化的影响。因此,前面的描述并非旨在将本发明限制于上文提出的特定示例,并且不应该被解释为将本发明限制于上文提出的特定示例。
Claims (19)
1.一种FCC添加剂组合物,其包含:
a.约35wt%至约80wt%的沸石;
b.约0wt%至约10wt%的二氧化硅粘合剂;
c.约7wt%至约20wt%的P2O5;
d.约10.5wt%至约20wt%的包含多于一种氧化铝源的氧化铝;
e.平衡粘土。
2.如权利要求1所述的添加剂,其中所述沸石选自MFI型沸石,MEL型沸石,MTW型沸石,MWW型沸石MCM-36、MCM-49、MCM-56,以及BEA型沸石或其混合物。
3.如权利要求2所述的添加剂,其中所述沸石是MFI型沸石。
4.如权利要求3所述的添加剂,其中所述沸石是ZSM-5。
5.如权利要求1所述的添加剂,其中P2O5源选自磷酸、磷酸二氢铵和磷酸氢二铵、连二磷酸铵、正磷酸铵、正磷酸二氢铵、正磷酸氢铵、磷酸三铵、膦和亚磷酸盐或其混合物。
6.如权利要求1所述的添加剂,其中所述氧化铝源包括至少一种大微晶氧化铝和至少一种小微晶氧化铝。
7.如权利要求6所述的添加剂,其中所述至少一种小微晶氧化铝的平均微晶尺寸为小于约10nm。
8.如权利要求6所述的添加剂,其中所述至少一种大微晶氧化铝的平均微晶尺寸为大于约15nm。
9.如权利要求6所述的添加剂,其中所述至少一种大微晶尺寸氧化铝的量为约0至约10wt%。
10.如权利要求6所述的添加剂,其中所述至少一种小微晶尺寸氧化铝的量为约2.5至约15wt%。
11.如权利要求6所述的添加剂,其中所述至少一种大微晶尺寸氧化铝源包括薄水铝石。
12.如权利要求6所述的添加剂,其中所述至少一种小微晶尺寸氧化铝源包括拟薄水铝石或氧化铝溶胶。
13.如权利要求1所述的添加剂,其中所述氧化铝源包括至少一种非薄水铝石氧化铝和至少一种小微晶氧化铝。
14.如权利要求13所述的添加剂,其中所述至少一种小微晶氧化铝的平均微晶尺寸为小于约10nm。
15.如权利要求13所述的添加剂,其中所述至少一种小微晶尺寸氧化铝的量为约2.5至约15wt%。
16.如权利要求13所述的添加剂,其中所述至少一种非薄水铝石氧化铝的量为约0至约10wt%。
17.如权利要求13所述的添加剂,其中所述至少一种非薄水铝石是三水铝石。
18.一种制备前述权利要求中任一项所述的添加剂的方法。
19.前述权利要求中任一项所述的催化剂添加剂在烃原料的催化裂化方法中的用途。
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BR112019017590A2 (pt) | 2020-03-24 |
CA3052674A1 (en) | 2018-09-20 |
WO2018170452A8 (en) | 2019-09-19 |
US20230149905A1 (en) | 2023-05-18 |
EP3595811A1 (en) | 2020-01-22 |
CN110300623B (zh) | 2023-08-11 |
WO2018170452A1 (en) | 2018-09-20 |
US11964256B2 (en) | 2024-04-23 |
JP2020514040A (ja) | 2020-05-21 |
JP7235670B2 (ja) | 2023-03-08 |
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