WO2014042641A1 - Novel catalyst to increase propylene yields from a fluid catalytic cracking unit - Google Patents
Novel catalyst to increase propylene yields from a fluid catalytic cracking unit Download PDFInfo
- Publication number
- WO2014042641A1 WO2014042641A1 PCT/US2012/055152 US2012055152W WO2014042641A1 WO 2014042641 A1 WO2014042641 A1 WO 2014042641A1 US 2012055152 W US2012055152 W US 2012055152W WO 2014042641 A1 WO2014042641 A1 WO 2014042641A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zeolite
- catalyst
- zsm
- beta
- phosphorus
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- 238000004231 fluid catalytic cracking Methods 0.000 title claims abstract description 30
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 22
- 239000010457 zeolite Substances 0.000 claims abstract description 208
- 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 202
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 189
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 29
- 229910052698 phosphorus Inorganic materials 0.000 claims description 55
- 239000011574 phosphorus Substances 0.000 claims description 55
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 52
- 239000000654 additive Substances 0.000 claims description 30
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- 230000000996 additive effect Effects 0.000 claims description 27
- 239000005995 Aluminium silicate Substances 0.000 claims description 26
- 235000012211 aluminium silicate Nutrition 0.000 claims description 26
- 229930195733 hydrocarbon Natural products 0.000 claims description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 23
- 238000005336 cracking Methods 0.000 claims description 23
- 239000004215 Carbon black (E152) Substances 0.000 claims description 21
- 239000004005 microsphere Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 230000001965 increasing effect Effects 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 description 32
- -1 olefin hydrocarbon Chemical class 0.000 description 21
- 150000001336 alkenes Chemical class 0.000 description 17
- 239000002253 acid Substances 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 238000004523 catalytic cracking Methods 0.000 description 13
- 239000002808 molecular sieve Substances 0.000 description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 150000002910 rare earth metals Chemical group 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000012013 faujasite Substances 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000003624 transition metals Chemical group 0.000 description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 101100456282 Caenorhabditis elegans mcm-4 gene Proteins 0.000 description 1
- NHEULQMXMXIOJY-UHFFFAOYSA-N Cl[PH2]=O Chemical class Cl[PH2]=O NHEULQMXMXIOJY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 229920000388 Polyphosphate Polymers 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical group [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 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
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect 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
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- DQTRYXANLKJLPK-UHFFFAOYSA-N chlorophosphonous acid Chemical class OP(O)Cl DQTRYXANLKJLPK-UHFFFAOYSA-N 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- ZDTQJPVEXIUREJ-UHFFFAOYSA-N dichlorophosphinous acid Chemical class OP(Cl)Cl ZDTQJPVEXIUREJ-UHFFFAOYSA-N 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- RDXABLXNTVBVML-UHFFFAOYSA-N diethoxyphosphanyl diethyl phosphite Chemical compound CCOP(OCC)OP(OCC)OCC RDXABLXNTVBVML-UHFFFAOYSA-N 0.000 description 1
- ZUKLAAHCPUBQLQ-UHFFFAOYSA-N diethylphosphinous acid Chemical compound CCP(O)CC ZUKLAAHCPUBQLQ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 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
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000007871 hydride transfer reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator 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 group 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- RYIOLWQRQXDECZ-UHFFFAOYSA-N phosphinous acid Chemical class PO RYIOLWQRQXDECZ-UHFFFAOYSA-N 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 229910052723 transition metal Chemical group 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-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
- 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
- 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
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- 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
- B01J29/80—Mixtures of different zeolites
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- B01J35/19—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/06—Propene
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/60—Synthesis on support
- B01J2229/64—Synthesis on support in or on refractory materials
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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
- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
Definitions
- the present invention provides a novel catalyst composition for increasing propylene yields during fluid catalytic cracking.
- Catalytic cracking and particularly fluid catalytic cracking (FCC) is routinely used to convert heavy hydrocarbon feedstocks to lighter products, such as gasoline and distillate range fractions.
- FCC fluid catalytic cracking
- Light olefins especially propylene
- Propylene for example, a light olefin hydrocarbon with three carbon atoms per molecule, is an important chemical for use in the production of other useful materials, such as polypropylene.
- Polypropylene is one of the most common plastics found in use today and has a wide variety of uses for both as a fabrication material and as a material for packaging.
- the catalytic cracking of heavy hydrocarbon feedstocks is typically carried out by contacting a naphtha- containing feed with a catalyst composition usually comprised of one or more crystalline microporous molecular sieves to selectively convert the feed into an olefin-containing mixture.
- a catalyst composition usually comprised of one or more crystalline microporous molecular sieves to selectively convert the feed into an olefin-containing mixture.
- FCC processes a hydrocarbon feedstock is injected into the riser section of a FCC reactor, where the feedstock is cracked into lighter, more valuable products upon contacting hot catalyst circulated to the riser-reactor from a catalyst regenerator.
- a major breakthrough in FCC catalysts came in the early 1960s, with the introduction of molecular sieves or zeolites. These materials were incorporated into the matrix of amorphous and/or amorphous/kaolin materials constituting the FCC catalysts of that time.
- zeolitic catalysts containing a crystalline aluminosilicate zeolite in an amorphous or amorphous/kaolin matrix of silica, alumina, silica-alumina, kaolin, clay or the like were at least ,000-10,000 times more active for cracking hydrocarbons than the earlier amorphous or amorphous/kaolin containing silica-alumina catalysts.
- This introduction of zeolitic cracking catalysts revolutionized the fluid catalytic cracking process. New processes were developed to handle these high activities, such as riser cracking, shortened contact times, new regeneration processes, new improved zeolitic catalyst developments, and the like.
- the zeolites typically used in FCC are crystalline aluminosilicat.es which have a uniform crystal structure characterized by a large number of regular small cavities interconnected by a large number of even smaller channels. It was discovered that, by virtue of this structure consisting of a network of
- crystalline zeolites are able to accept, for absorption, molecules having sizes below a certain well defined value while rejecting molecules of larger sizes, and for this reason they have come to be known as "molecular sieves.” This characteristic structure also gives them catalytic properties, especially for certain types of hydrocarbon
- the ZSM family of zeolites is well known and their preparation and properties have been extensively described in the catalytic cracking of hydrocarbons.
- one type of the ZSM family of zeolites is that known as ZSM-5.
- the crystalline aluminosilicate zeolite known as ZSM-5 is particularly described in U.S. Pat. No. 3,702,886, the disclosure of which is incorporated herein by reference.
- ZSM-5 crystalline aluminosilicate is characterized by a silica-to-alumina mole ratio of greater than 5 and more precisely in the anhydrous state by the general formula: [0.9.+- .0.2 .2 nO:Al2O3: 5SiO2] wherein M having a valence n is selected from the group consisting of a mixture of alkali metal cations and organo ammonium cations, particularly a mixture of sodium and tetraalkyl ammonium cations, the alkyl groups of which preferably contain 2 to 5 carbon atoms.
- M having a valence n is selected from the group consisting of a mixture of alkali metal cations and organo ammonium cations, particularly a mixture of sodium and tetraalkyl ammonium cations, the alkyl groups of which preferably contain 2 to 5 carbon atoms.
- anhydrous as used in the above context means that molecular water is not included in the formula.
- the mole ratio of S1O2 to AI2O3 for a ZSM-5 zeolite can vary widely.
- ZSM-5 zeolites can be aluminum-free in which the ZSM-5 is formed from an alkali mixture of silica containing only impurities of aluminum. All zeolites characterized as ZSM-5, however, will have the characteristic X-ray diffraction pattern set forth in U.S. Pat. No. 3,702,886 regardless of the aluminum content of the zeolite.
- Beta zeolite is another zeolite that can be used in the catalytic cracking of hydrocarbons.
- Beta zeolite is typically a silicon-rich large pore zeolite having a three-dimensional pore structure, and has both acid catalytic properties and structural selectivity due to its structural particularity, and further has very high thermostability (the failure temperature of the crystal lattice is higher than 1200 S C), hydrothermal stability and abrasion-resistant properties. Due to the unique structural features, thereof, the zeolite beta has good thermal and hydrothermal stability, acid resistance, anti-coking properties and catalytic activity in a series of catalytic reactions. It has thus developed rapidly for new catalytic processes in recent years.
- the catalysts used in FCC processing have been tailored to maximize the performance in specific hydrocarbon conversion processes.
- the catalyst compositions used in hydrocarbon conversion processes have been made into multifunctional catalysts, e.g., a bifunctional catalyst or a trifunctional catalyst.
- a bifunctional catalyst comprises two separate catalysts, e.g., two zeolites having different compositions or structure types, which induce separate reactions.
- the reaction products can be separate or the two catalysts can be used together such that the reaction product of one catalyst is transported to and reacts on a catalyst site of the second catalyst.
- zeolite catalysts used in hydrocarbon conversion processes have the capability of preventing or at least reducing unwanted reactions which may take place on the surface of the zeolite catalyst by selectively sieving molecules in the feedstream based on their size or shape.
- undesirable molecules present in the feedstream are prevented from entering the pores of the catalyst and reacting.
- the performance of a zeolite catalyst can sometimes be maximized if the catalyst selectively sieves desired molecules based on their size or shape in order to prevent the molecules from exiting the pores of the catalyst.
- a catalyst composition containing a large pore molecular sieve, such as zeolite Y, as the primary cracking component and a medium pore zeolite, such as ZSM-5, added to the zeolite Y cracking catalyst is typically used in conventional processes for catalytic cracking of heavy hydrocarbon feedstocks to gasoline and distillate fractions.
- U.S. Patent No. 3,758,403 discloses a catalyst using ZSM-5 zeolite and a large pore zeolite such as zeolite Y (with a ratio of 1 :10 to 3:1) as active components.
- this catalyst mixture provides a higher yield of C3 and C 4 olefins.
- CN 1 103105A and EP-2-075-068 A1 describe the use of catalyst compositions comprising three different zeolites in hydrocarbon cracking.
- CN 1 103105A discloses a cracking catalyst capable of giving a higher yield of isobutene and isopentene than without the catalyst and can coproduce high octane level gasoline.
- the components and contents of the catalyst described in CN 1 103105A are as follows: (1) 5-25 wt.% modified HZS -5 with a
- EP-2-075-068 A1 describes a catalyst composition with a zeolite mixture as follows: (1 ) 1-75 wt.% of a zeolite beta modified with phosphorus and a transition metal; (2) 25-99 wt.% of a zeolite having a MFI structure, such as ZSM- 5; and (3) 0-74 wt.% of a large pore zeolite, such as a Y zeolite.
- a zeolite cracking catalyst with added phosphorus has been used.
- WO 98/41595 discloses that the addition of a phosphorus-containing, medium pore zeolite, such as ZSM-5, to a conventional large pore molecular sieve cracking catalyst increases the yield of C3 to C5 olefins in the catalytic cracking of hydrocarbon feedstocks without significant loss in the aging characteristics of the medium pore additive.
- the yield of C 4 and C 5 olefins in catalytic cracking can be enhanced by adding a phosphorus-containing medium pore zeolite, such as ZSM-5, to a conventional zeolite Y cracking catalyst.
- Incorporation of the phosphorus in the medium pore zeolite is conveniently achieved by the methods described in U.S. Patent Nos. 4,356,338, 5,110,776, and 5,231 ,064.
- Treatment with phosphorus-containing compounds can readily be accomplished by contacting the zeolite, either alone or in combination with a binder or matrix material, with a solution of an appropriate phosphorus compound, followed by drying and calcining to convert the phosphorus to its oxide form.
- the objective of this invention is to develop a petrochemical fluid catalytic cracking catalyst blend that results in a significant increase in propylene yield compared to the current state of the art petrochemical FCC catalyst systems.
- This invention supplements known blends of Y zeolite and ZSM-5, with an additional additive containing Beta zeolite.
- the objective of this invention is to develop a petrochemical FCC catalyst system that results in a significant increase in propylene yield compared to the current state of the art petrochemical FCC catalyst systems.
- Current petrochemical catalyst systems typically consist of a blend of a large pore catalyst, such as a Y zeolite based FCC catalyst, and an additive zeolite, such as ZSM-5. This invention proposes supplementing the current catalyst blend with an additional additive containing Beta zeolite.
- the present invention provides a catalyst blend, which comprises, based on the total weight of the catalyst blend, 5-50 wt.% zeolite Y, 5-40 wt.% ZSM-5, and 35-70% Beta catalyst.
- the catalyst composition comprises 25-30 wt.% zeolite Y, 15-20 wt.% ZSM-5, and 50-60% Beta catalyst.
- the weight percent for each zeolite as expressed immediately above and hereafter, including the appended claims, pertains to the active zeolite component and any matrix, binder or additive components.
- FCC catalysts are often blends of a catalytically active large-pore zeolite component and additives containing other zeolites.
- Large pore cracking catalysts have pore openings of greater than about 7 Angstroms in effective diameter.
- Conventional large-pore molecular sieves include zeolite X ⁇ U.S. Pat. No. 2,882,442); REX; zeolite Y (U.S. Pat. No. 3,130,007); Ultrastable Y (USY) (U.S. Pat. No. 3,449,070); Rare Earth exchanged Y (REY) (U.S. Pat. No.
- pillared silicates and/or clays include pillared silicates and/or clays; aluminophosphates, e.g., AIPO.sub.4-5, AIPO.sub.4-8, VPI-5; silicoaluminophosphates, e.g., SAPO-5, SAPO-37, SAPO-40, MCM-9; and other metal aluminophosphates.
- Mesoporous crystalline material for use as the molecular sieve includes MCM-4 . These are variously described in U.S. Pat. Nos. 4,310,440; 4,440,871 ; 4,554,143; 4,567,029; 4,666,875; 4,742,033;
- the preferred molecular sieve of those listed above is a zeolite Y, more preferably a REY, USY or REUSY.
- the zeolite Y is incorporated into an amorphous binder as is well known in the art.
- Suitable binders include silica, silica-alumina, alumina, clay or other known inorganic binders.
- zeolite Y could be produced into high zeolite content microspheres by the in-situ procedure described in U.S. Patent No. 4,493,902, the teachings of which are incorporated herein by cross- reference.
- the '902 patent discloses novel fluid cracking catalysts comprising attrition-resistant, high zeolitic content, catalytically active microspheres containing more than about 40%, preferably 50-70% by weight Y faujasite and methods for making such catalysts by crystallizing more than about 40% sodium Y zeolite in porous microspheres composed of a mixture of metakaolin (kaolin calcined to undergo a strong endothermic reaction associated with
- microspheres containing the two forms of calcined kaolin could also be immersed in an alkaline sodium silicate solution, which is heated, preferably until the maximum obtainable amount of Y faujasite is crystallized in the microspheres.
- microspheres composed of kaolin calcined to undergo the exotherm and metakaolin are reacted with a caustic enriched sodium silicate solution in the presence of a crystallization initiator (seeds) to convert silica and alumina in the microspheres into synthetic sodium faujasite (zeolite Y).
- seeds crystallization initiator
- the microspheres are separated from the sodium silicate mother liquor, ion-exchanged with rare earth, ammonium ions or both to form rare earth or various known stabilized forms of catalysts.
- the technology of the '902 patent provides means for achieving a desirable and unique combination of high zeolite content associated with high activity, good selectivity and thermal stability, as well as attrition-resistance.
- zeolite Y could be produced as novel zeolite microspheres, known as the Naphthamax® catalyst from BASF Catalysts, which are disclosed in U.S. Patent No. 6,656,347.
- These zeolite microspheres are macroporous, have sufficient levels of zeolite to be very active and are of a unique morphology to achieve effective conversion of hydrocarbons to cracked gasoline products with improved bottoms cracking under short contact time FCC processing.
- the novel zeolite microspheres are produced by novel processing, which is a modification of technology described in the '902 patent.
- non-zeolite, alumina-rich matrix of the catalyst is derived from an ultrafine hydrous kaolin source having a particulate size such that 90 wt. % of the hydrous kaolin particles are less than 2 microns, and which is pulverized and calcined through the exotherm, a macroporous zeolite
- the FCC catalyst matrix useful to achieve FCC catalyst macroporosity is derived from alumina sources, such as kaolin calcined through the exotherm, that have a specified water pore volume, which distinguishes over prior art calcined kaolin used to form the catalyst matrix.
- the water pore volume is derived from an Incipient Slurry Point (ISP) test, which is described in the patent.
- microsphere catalysts which are formed is unique relative to the in-situ microsphere catalysts formed previously.
- Use of a pulverized, ultrafine hydrous kaolin calcined through the exotherm yields in-situ zeolite microspheres having a macroporous structure in which the macropores of the structure are essentially coated or lined with zeolite subsequent to
- Macroporosity as defined herein means the catalyst has a macropore volume in the pore range of 600-20,000 angstroms of at least 0.07 cc/gm mercury intrusion, preferably at least 0.10 cc/gm mercury intrusion.
- the novel catalyst is optimal for FCC processing, including the short contact time processing in which the hydrocarbon feed is contacted with a catalyst for times of about 3 seconds or less.
- the Naphthamax® as described in U.S. Patent No. 6,656,347 is not restricted to macroporous catalysts having a non-zeolite matrix derived solely from kaolin.
- any alumina source which has the proper combinations of porosity and reactivity during zeolite synthesis and can generate the desired catalyst macroporosity and morphology can be used.
- the desired morphology comprises a matrix which is well dispersed throughout the catalyst, and the macropore walls of matrix are lined with zeolite and are substantially free of binder coatings.
- the zeolite crystals are readily accessible to the hydrocarbon feed. While not wishing to be bound by any theory of operation, it appears that previous catalysts in which the zeolite is incorporated into a matrix by physical mixing and glued with binder have sufficient macroporosity, however the binder coats the active zeolite catalyst thereby blocking accessibility thereto.
- the Naphthamax® microsphere catalysts have a morphology which allows fast diffusion into the catalyst due to the macroporosity and enhanced dispersion of the matrix, and further provides the highest accessibility to the zeolite inasmuch as the zeolite is freely coated onto the walls of the pores.
- the term "freely” means that the zeolite phase is present on the surface of the matrix and is unobstructed by any binder phases.
- macroporosity does not provide the results that have been obtained, since conventional incorporated catalysts have similar macroporosity. It is therefore the combination of porosity and zeolite-coated macropore walls that give the surprising selectivity results.
- zeolite Y is a rare earth exchanged Y zeolite crystallized in-situ in a porous kaolin matrix. In another embodiment of the invention, zeolite Y contains up to 12% of a rare earth element ion exchanged onto the Y zeolite.
- ZSM-5 is blended with the Y zeolite. Based on the unique pore structure of ZSM-5, this zeolite can be applied extensively as a catalyst material to various processes. Zeolite ZSM-5 has been shown to be a particularly useful catalyst in reactions involving aromatic compounds, with emphasis on those having a single carbocycle. Thus ZSM-5 exhibits unique selectivity in the conversion of olefins, naphthenes, alcohols, ethers and alkanes into aromatic compounds and in such reactions as isomerization, alkylation, dealkylation and transalkylation of aromatics. That favorable influence on aromatic conversion reactions is found also in the forms of ZSM-5 in which another metal appears in isomorphic substitution for aluminum, as described in U.S. Pat. No.
- ZSM-5 has also been extensively applied in catalytic cracking and catalytic dewaxing.
- ZSM-5 has been used in catalytic cracking of petroleum, enhancement of gasoline octane is achieved. Accordingly, ZSM-5 has been used as an additive to other cracking catalysts, e.g. zeolite Y, to improve gasoline octane and LPG yields.
- the ZSM-5 zeolite additive is prepared as a separate microsphere and contains phosphorus stabilized ZSM-5 zeolite, alumina, and kaolin bound together with phosphoric acid.
- the ZSM-5 can be modified using phosphorus-containing compounds.
- Any phosphorus-containing compound having a covalent or ionic constituent capable of reacting with hydrogen ion may be employed such as, for example, phosphoric acid, phosphines and phosphites.
- These compounds include primary, RPH 2 , secondary, R 2 PH, and tertiary, R 3 P, phosphines such as butyl phosphine; the tertiary phosphine oxides, R 3 PO, such as tributylphosphine oxide; the primary RP(0)(OX) 2 and secondary R 2 P(0)OX, phosphonic acids such as benzene phosphonic acid; the esters of the
- phosphonic acids such as diethyl phosphonate, ⁇ RO) 2 P(0)H, dialkyi alkyl phosphonates, (RO) 2 P(0)R, and alkyl dialkytphosphinates, (RO)P(0)R 2 ;
- phosphinous acids such as diethylphosphinous acid, primary
- esters thereof such as the monopropyl ester, alkyl dialkylphosphinites, ⁇ RO)PR 2 and dialkyi alkylphosphonite, (RO) 2 PR esters.
- phosphite esters include trimethylphosphite, triethylphosphite, diisopropylphosphite, butylphosphite; and pyrophospites such as tetraethylpyrophosphite.
- the alkyl groups in the mentioned compounds contain 1 to 4 carbon atoms.
- Suitable phosphorus-containing compounds include the phosphorus halides such as phosphorus trichloride, bromide and iodide, alkyl
- Preferred phosphorus-containing compounds include: phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, or ammonium polyphosphate, trimethyl phosphite and phosphorus trichloride.
- the constituent of the phosphorus-containing compound capable of reacting with a hydrogen ion reacts with the hydrogen of the original zeolite.
- the phosphorus may be chemically bonded to the crystal structure of the zeolite since phosphorus-containing zeolites can be used for extended periods of time at high temperatures without loss of phosphorus.
- the phosphorus is present as a crystalline framework constituent, i.e., it has not been substituted for silicon or aluminum atoms, since the unit cell dimensions of the zeolite are unchanged on
- incorporation of the phosphorus atoms. Incorporation of the phosphorus with the zeolite provides a composition having unique properties as a catalytic agent.
- the zeolites possess strong acid sites.
- the phosphorus-containing zeolite does not possess these strong acid sites.
- the phosphorus-containing zeolite possesses a greater number of acid sites than the parent zeolite but these sites appear to have a lesser acid strength than those found in the parent zeolite. It is believed that the apparent replacement of the strong acid sites with a greater number of relatively weak acid sites may be responsible for the unique catalytic properties of the phosphorus-containing zeolite.
- Reaction of the zeolite with the phosphorus-containing compound is effected by contact.
- the phosphorus-containing compound is a liquid
- said compound can be in solution in a solvent at the time contact with the zeolite is effected.
- Any solvent relatively inert with respect to the phosphorus-containing compound and the zeolite may be employed. Suitable solvents include aliphatic, aromatic or alcoholic liquids.
- the phosphorus-containing compound is trimethylphosphite or liquid phosphorus trichloride, a hydrocarbon solvent such as n-octane may be employed.
- the phosphorus-containing compound may be used without a solvent, i.e., may be used as a neat liquid.
- the phosphorus-containing compound is in the gaseous phase, such as where gaseous phosphorus trichloride is employed, the phosphorus-containing compound can be used by itself or can be used in admixture with a gaseous diluent relatively inert to the phosphorus-containing compound and the zeolite such as air or nitrogen.
- the zeolite is dried prior to reacting the zeolite with the phosphorus-containing compound. Drying can be effected in the presence of air. Elevated temperatures may be employed. However, the temperature should not be such, as mentioned hereinafter, that the crystal structure of the zeolite is destroyed.
- Heating of the phosphorus-containing catalyst subsequent to preparation and prior to use is also preferred.
- the heating can be carried out in the presence of oxygen, for example air. Heating can be at a temperature of about 150 Q C. However, higher temperatures, i.e., up to about 500 Q C. are preferred. Heating can be carried out for 1-24 hours. It has been found that heating increases the catalyst efficiency of the phosphorus-containing zeolite probably due to an increase in the number of acid sites rather than an increase in the strength of the existing acid sites. Increasing the heating temperature increases the catalyst efficiency. However, while heating temperatures above about 500 B C. can be employed, they are not necessary. At temperatures of about 1000 B C, the crystal structure of the zeolite is destroyed.
- the amount of phosphorus incorporated with the crystal structure of the phosphorus-containing zeolite should be at least 0.1% by weight. With this amount of phosphorus, replacement of a sufficient proportion of the strong acid sites of the zeolite with an increased number of weaker acid sites is effected. In order to accomplish this it is preferred that the amount of phosphorus in the phosphorus-containing zeolite be at least about 0.5% by weight.
- the amount of phosphorus can be as high as 10% by weight, although with these higher amounts a decline in catalytic activity can occur.
- the large-pore molecular sieve catalyst component described above may also include phosphorus or a phosphorus compound for any of the functions generally attributed thereto.
- ZSM-5 selectively cracks gasoline range aliphatic molecules to form additional light olefins at the penalty of gasoline yield.
- the yields of 2-methyl- butenes and n-butenes also increase when using phosphorus-containing ZSM-5 as the additive, due to its more moderate acid strength.
- Untreated ZSM-5 will further crack these C 5 and C 4 olefins due to its high acid strength.
- the ZSM-5 zeolite is blended with the Y zeolite wherein the ZSM-5 zeolite additive is prepared according to U.S. Patent No. 7,375,048. According to the ⁇ 48 patent, a high solids kaolin slurry is mixed with a slurry containing ZSM-5, a high surface area alumina
- the mixed slurry is pumped to a static mixture adjacent to the atomizer of a spray dryer.
- Phosphoric acid is then injected into the dispersed high solids mixed kaolin slurry and the acid-injected slurry is atomized into droplets in a spray dryer.
- the process provides microspheres which have good kaolin interparticie binding and excellent physical and chemical properties. Moreover, the microspheres can contain at least 30 wt.% ZSM-5 and due to the addition of the unreactive alumina or other high density, unreactive inorganic material, have high attrition resistance.
- Beta zeolite is added to the Y zeolite and ZSM-5 zeolite blend.
- Beta zeolite is a crystalline zeolite whose composition and X-ray powder diffraction analysis are disclosed in U.S. Pat. Re No. 28,341 , herein incorporated by reference in its entirety. This zeolite is a large pore zeolite having a pore size above 7.0 angstroms and a Constraint Index below 2.
- Beta zeolite is prepared, in general, as an aluminosilicate zeolite having a silica-to- alumina molar ratio (S1O2/AI2O3) of at least 10.
- Beta zeolite is meant to encompass such materials.
- Beta zeolite is usually synthesized from a reaction mixture containing a templating agent.
- templating agents for synthesizing beta zeolite is well known in the art.
- U.S. Pat. No. 3,308,069 and Re No. 28,341 describe using tetraethylammonium hydroxide
- U.S. Pat. No. 5,139,759 which is hereby incorporated herein by reference in its entirety, describes using the tetraethylammonium ion derived from the corresponding tetraethylammonium halide.
- Another standard method of preparing beta zeolite is described in the book titled Verified Synthesis of Zeolitic Materials, by H. Robson (editor) and K. P. Gebrud ⁇ XRD Patterns), second revised edition, ISBN 0-444-50703-5,
- the beta zeolite is calcined in air at a temperature of from 500 to 700 B C for a time sufficient to remove to remove the templating agent from the beta zeolite.
- Calcination to remove the templating agent can be done before or after the beta zeolite is combined with the support and/or the hydrogenation component.
- the templating agent could be removed at calcination temperatures above 700 e C. Very high calcination temperatures could significantly decrease the SF 6 adsorption capacity of beta zeolite. For this reason it is believed that calcination temperatures above 750 S C for removing the templating agent should be avoided when preparing the beta zeolite for use in the process disclosed herein. It is critical to the process disclosed herein that the SF 6 adsorption capacity of the beta zeolite is at least 28 wt-%.
- Beta zeolite additive for the present invention is prepared similar to the ZSM-5 additive and according to U.S. Patent No.
- the form of the Beta zeolite is as H-Beta with a silica/alumina ratio greater than 10, further exemplified by silica/alumina ratios greater than 35.
- the silica/alumina ratio of the H-Beta zeolite can also be greater than 100.
- Stabilization of the Beta zeolite with phosphorus in the present invention can be achieved by direct reaction of Beta zeolite with phosphoric acid or by incorporating the phosphoric acid into the additive via direct injection during the spray drying process.
- Ammonium hydrogen phosphates, or polyphosphate as described earlier for the ZSM-5 additive can also be used.
- the phosphorus level on the Beta zeolite is between 1 and 7% P2O5.
- the phosphorus level on the Beta zeolite is between 3 and 5% P 2 0 5 .
- Adding the phosphoric acid via inline injection during spray drying of the Beta additive required a preferred total phosphorus level of between 10 and 15% P 2 0 5 with a more preferred level of 12-13% P 2 0 5 .
- the Y zeolite is Naphthamax® (rare earth exchanged Y zeolite crystallized in situ in a porous kaolin matrix) and is blended with the additive containing ZSM-5 zeolite, described above.
- Beta zeolite has a high propensity to make olefins due to its low intrinsic hydride transfer capability. This can be observed in the high levels of isobutylene to isobutane in cracking reactions. Blend ratios for maximum propylene yield therefore are based on more Beta additive than
- Naphthamax® and more Naphthamax® than ZSM-5 additive Such a formulation would be 50-60% Beta additive, 25-30% 1% REO Naphthamax® and 15-20% ZSM-5 additive. Such a formulation gives propylene yields 1 .5-2.5% higher than with the current state of the art Petrochemical FCC catalyst.
- a catalyst composition comprised of a blend of 60% Beta additive, 25% 1 % REO Naphthamax and 5% ZSM-5 additive was prepared.
- the propylene yield of this catalyst composition is compared with a prior art Petrochemical FCC catalyst containing 23.5% ZSM-5 additive and 76.5% 1 % REO Naphthamax.
- ACE testing using Reliance feed gave an increase in propylene yield of over 2%.
Abstract
Description
Claims
Priority Applications (9)
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KR1020147009378A KR20140090597A (en) | 2011-09-13 | 2012-09-13 | Novel catalyst to increase propylene yields from a fluid catalytic cracking unit |
CN201280055630.8A CN103945940A (en) | 2011-09-13 | 2012-09-13 | Novel catalyst to increase propylene yields from a fluid catalytic cracking unit |
RU2014114379A RU2612973C2 (en) | 2012-09-13 | 2012-09-13 | Novel catalyst to increase propylene yields from fluid catalytic cracking unit |
CA2845414A CA2845414A1 (en) | 2011-09-13 | 2012-09-13 | Novel catalyst to increase propylene yields from a fluid catalytic cracking unit |
BR112014005898A BR112014005898A2 (en) | 2011-09-13 | 2012-09-13 | hydrocarbon conversion catalyst |
MX2014002923A MX342783B (en) | 2011-09-13 | 2012-09-13 | Novel catalyst to increase propylene yields from a fluid catalytic cracking unit. |
EP12884592.2A EP2755763A4 (en) | 2011-09-13 | 2012-09-13 | Novel catalyst to increase propylene yields from a fluid catalytic cracking unit |
JP2015531895A JP6133989B2 (en) | 2011-09-13 | 2012-09-13 | A novel catalyst to increase propylene yield from fluid catalytic cracking unit |
IN2684CHN2014 IN2014CN02684A (en) | 2012-09-13 | 2014-04-09 |
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US13/231,522 | 2011-09-13 | ||
US201213231522A | 2012-09-13 | 2012-09-13 |
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IN (1) | IN2014CN02684A (en) |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US10494574B2 (en) | 2017-02-23 | 2019-12-03 | Saudi Arabian Oil Company | Systems and methods for cracking hydrocarbon streams such as crude oils utilizing catalysts which include zeolite mixtures |
US10526546B2 (en) | 2017-02-23 | 2020-01-07 | Saudi Arabian Oil Company | Systems and methods for cracking hydrocarbon streams utilizing cracking catalysts |
CN113526521A (en) * | 2020-04-13 | 2021-10-22 | 中国石油化工股份有限公司 | Molecular sieve composite of phosphorus modified ZSM-5 and Y |
WO2022026878A1 (en) * | 2020-07-31 | 2022-02-03 | Basf Corporation | Fluid catalytic cracking catalyst composition for enhanced butylene to propylene selectivity ratio |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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RU2688662C1 (en) * | 2018-07-24 | 2019-05-22 | Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (Институт катализа СО РАН, ИК СО РАН) | Method of catalytic cracking of butane-butylene fraction and catalyst for its implementation |
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IN2014CN02684A (en) | 2015-07-03 |
RU2014114379A (en) | 2016-11-10 |
RU2612973C2 (en) | 2017-03-14 |
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