CN103842318A - 用于烃转化的催化剂及方法 - Google Patents
用于烃转化的催化剂及方法 Download PDFInfo
- Publication number
- CN103842318A CN103842318A CN201280049036.8A CN201280049036A CN103842318A CN 103842318 A CN103842318 A CN 103842318A CN 201280049036 A CN201280049036 A CN 201280049036A CN 103842318 A CN103842318 A CN 103842318A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- crystallinity
- catalyzer
- particle
- granules
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 title description 23
- 150000002430 hydrocarbons Chemical class 0.000 title description 23
- 239000004215 Carbon black (E152) Substances 0.000 title description 15
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 28
- 239000011148 porous material Substances 0.000 claims abstract description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 54
- 239000002245 particle Substances 0.000 claims description 36
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 33
- 239000010457 zeolite Substances 0.000 claims description 30
- 229910021536 Zeolite Inorganic materials 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 15
- 150000003738 xylenes Chemical class 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 230000009466 transformation Effects 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 230000001131 transforming effect Effects 0.000 claims description 9
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 7
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 32
- 229940058172 ethylbenzene Drugs 0.000 description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 29
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 229910052697 platinum Inorganic materials 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000001354 calcination Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000008096 xylene Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- -1 aluminum alkoxide Chemical class 0.000 description 6
- 239000011959 amorphous silica alumina Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 229910052702 rhenium Inorganic materials 0.000 description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 4
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-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
- 239000003607 modifier Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000006187 pill Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001398 aluminium Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003171 wood protecting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
-
- 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
- B01J29/42—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 containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J37/12—Oxidising
-
- 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
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/073—Ethylbenzene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/08—Xylenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—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
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/22—Noble metals
-
- 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
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
- B01J29/67—Noble metals
-
- 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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
-
- 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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7446—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
-
- 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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7469—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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7476—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
- 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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7484—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
-
- 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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7492—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明包括一种烃转化方法,该方法使用包含极低浓度的非沸石材料的沸石催化剂及其特征为结晶度从外部至中心减小的梯度及至少0.6cc/克的侵入孔体积。该催化剂特定而言在包括乙苯转化的二甲苯异构方法中具有效性。
Description
优先权声明
本申请主张2011年11月1日提交的美国申请第13/286,553号的优先权。
发明领域
本发明涉及用于烃转化的催化剂及方法。更特定而言,本发明揭示用于有效转化乙苯及异构化二甲苯的催化剂。
背景技术
沸石被广泛地作为催化剂用于多种类型的烃转化方法,诸如异构化、重整、氢化、烷基化、烷基转移、裂化及加氢裂化。另外,沸石材料被作为吸附剂用于多种石油及化学品分离方法。催化或分离作用的选择性是由结晶铝硅酸盐网络所形成的间隙空间或通道所赋予。沸石亦可包括其中已完全或部分地以其它氧化物替换氧化硅及氧化铝部分的材料;氧化锗、氧化锡及其混合物可替换氧化硅部分及氧化镓、氧化铟、氧化硼、氧化铁及其混合物可替换氧化铝部分。
纯沸石的实际应用因机械强度限制而严格受限。机械强度可通过在非沸石粘合剂存在下形成沸石并干燥和煅烧所得挤出物丸粒、球或挤出物而赋予。这些粘合剂的实例包括材料,如氧化铝、氧化硅、钛及不同类型粘土。然而,因为粘合剂会减弱沸石的吸附性质,故结合的沸石就活性、选择性或活性维持而言的有效性会减低。另外,由于结合的沸石是通过使沸石与粘合剂一起挤出接着干燥和煅烧该挤出物而制备,故非晶形粘合剂可渗入沸石的孔隙,或者阻塞这些沸石孔的进口,或减慢传输至沸石孔的传质速率,这会减低沸石的有效性。再者,当将结合的沸石用于催化方法时,粘合剂会影响在沸石中发生的化学反应及亦可能催化不期望的反应而可能导致形成不想要的产物。
沸石催化剂的主要应用是转化C8芳族化合物以获得各二甲苯异构体。二甲苯、对二甲苯、间二甲苯及邻二甲苯为在化学合成中具有宽广及多种应用的重要中间体。对二甲苯在氧化时生成用于制造合成织物纤维及树脂的对苯二甲酸。间二甲苯是用于制造塑化剂、偶氮染料、木材防腐剂等。邻二甲苯为用于制造邻苯二甲酸酐的原料。
石油石脑油的催化重整是C8芳族化合物的重要来源。催化重整或其它来源的C8芳族化合物中的二甲苯异构体一般不匹配作为化学中间体的需求比例,且进一步包含难以分离或转化的乙苯。对二甲苯特定而言为其需求快速增长的主要化学中间体,但其量仅占典型C8芳族化合物料流的15至20%。调整异构体比率以达需求可通过组合二甲苯异构体回收(诸如针对对二甲苯回收的吸附)与异构化以产生额外量的期望异构体来实现。异构化使所期望二甲苯异构体贫乏的二甲苯异构体的非平衡混合物转化为接***衡浓度的混合物。所利用到平衡的路径是高转化率(即,极其接***衡)下的高C8环状化物损耗与由于未经转化的C8芳族化合物的大再循环速率所致的高公用事业成本之间的最优化折衷。
用于转化C8芳族化合物的方法通常是以转化与二甲苯异构体相关联的乙苯的方式分类。乙苯不易异构化为二甲苯,但其通常在方法单元中转化,因为通过超精馏或吸附将其从二甲苯分离的成本极高。一种方法是通过在具有氢化-脱氢功能的固体酸催化剂存在下转化成环烷烃及从环烷烃再转化而使乙苯反应形成二甲苯混合物。另一种广泛采用的方法是使乙苯脱烷基化以主要形成苯,同时使二甲苯异构化为***衡混合物。前一方法通过从乙苯形成二甲苯从而提高二甲苯产率;后一方法通常达成较高的乙苯转化率,因而降低再循环至对二甲苯回收单元的量及减低附随的处理成本。
氢一般存在于转化方法反应物中以帮助反应及维持催化剂稳定性。虽然二甲苯于一些情况下可在无氢存在下异构化从而节省费用,但乙苯转化通常需要存在氢。于一些情况中两阶段处理单元可经证实对达成高转化率及乙苯产率适用。无论如何,仍继续寻找更有效的催化剂及方法。
发明简述
本发明的主要目标是提供一种有效用于转化烃的新颖催化剂。更特定而言,本发明包括一种用于转化烷基芳族烃及特定而言用于处理C8芳族化合物以增加期望二甲苯异构体的浓度且降低芳族化合物损耗及降低处理成本的方法。
本发明是基于发现可通过包含具有特定孔隙率及结晶度梯度特征的无粘合剂沸石的催化剂进行与二甲苯异构化相关联的乙苯转化。
因此,本发明的一个实施方案是一种用于转化非平衡C8-芳族化合物原料的方法,该方法包括使原料与包含非结合沸石铝硅酸盐颗粒的催化剂床接触,所述颗粒具有至少0.65cc/克的颗粒侵入孔体积及结晶度比例从低结晶度内部至高结晶度外部增加的颗粒结晶度梯度,该接触在转化区中以包括340℃至500℃的温度、100kPa至5MPa的压力及2至50hr-1的质量时空间速度的转化条件在氢存在下进行,以使乙苯转化及获得异构化产物,该异构化产物含有比在原料中更高比例的至少一种二甲苯异构体。
一个更特定实施方案是一种用于转化非平衡C8-芳族原料的方法,该方法包括使原料与包含非结合沸石铝硅酸盐颗粒的催化剂床接触,所述颗粒具有至少0.65cc/克的颗粒侵入孔体积及结晶度比例从具有10至50重量%的相对结晶度的内部增加至具有90至100重量%的相对结晶度的高结晶度500微米外部的颗粒结晶度梯度,该接触在转化区中以包括340℃至500℃的温度、100kPa至5MPa的压力及2至50hr-1的质量时空间速度的转化条件在氢存在下进行,以使乙苯转化及获得异构化产物,该异构化产物含有比在原料中更高比例的至少一种二甲苯异构体。
又一更特定实施方案是一种用于转化非平衡C8-芳族原料的方法,该方法包括使原料与包含非结合沸石铝硅酸盐颗粒的催化剂床接触,所述颗粒具有至少0.65cc/克的颗粒侵入孔体积及结晶度比例从具有10至50重量%的相对结晶度的内部增加至具有90至100重量%的相对结晶度的高结晶度100微米外部的颗粒结晶度梯度,该接触在转化区中以包括340℃至500℃的温度、100kPa至5MPa的压力及2至50hr-1的质量时空间速度的转化条件在氢存在下进行,以使乙苯转化,且每%乙苯转化,二甲苯损耗小于0.02,及获得异构化产物,该异构化产物含有比原料中更高比例的至少一种二甲苯异构体。
可从本发明的以下详细论述明了其它特定实施方案。
附图简述
图1显示本发明颗粒的特征。
发明详述
本发明的无粘合剂球形沸石颗粒的特征为针对烃转化及尤其是针对芳族烃转化的高催化活性及选择性。本发明含沸石催化剂的实例包括Si:Al2比大于10及通常大于20的那些,诸如MFI、MEL、EUO、FER、MFS、MTT、MTW、TON、MOR及FAU类型的沸石作为骨架类型,如Atlas ofZeolite Framework Types,修改版第6版,C.H.Baerlocher、L.B.McCusker及D.H.Olson编辑,Elsevier(2007)中所述。Pentasil沸石(如MFI、MEL、MTW及TON)为优选,及MFI型沸石(如ZSM-5、疏水硅沸石(silicalite)、Borolite C、TS-1、ZSM-12、SSZ-25、PSH-3及ITQ-1)为最优选。
制备本发明的优选催化剂首先包括形成铝及硅的反应混合物。铝的来源包括(但不限于)烷氧基铝、沉淀氧化铝、铝金属、铝盐及氧化铝溶胶。烷氧基铝的特定实例包括(但不限于)仲丁醇铝及邻异丙醇铝。氧化硅的来源包括(但不限于)原硅酸四乙酯、胶态二氧化硅、沉淀二氧化硅、碱硅酸盐、HiSil及Ultrasil。Si/Al比可为3至100,及优选为8至50。
优选地,氧化硅-氧化铝混合物实质上不含如上文所述的沸石或如下文所述的结构导向剂,然而,于本发明的范畴内,这些物质可相对少量地存在。
一种优选方法包括通过本领域已知方法制造非晶形氧化硅-氧化铝。例如,可使用阐述于以引用方式并入的US3,909,450中的方法。该方法涉及在回流温度下于盐酸水溶液中蒸煮铝以制备铝溶胶,从而形成具有预定铝/氯化物比的溶胶。将该铝溶胶与已(例如)通过酸化水玻璃制得的硅溶胶混合。添加胶凝剂(如六亚甲基四胺、脲或其混合物)且溶胶混合物呈液滴分散在其中发生胶凝化伴随形成球形颗粒的热油浴中。胶凝剂使溶胶液滴的pH提高,致使这些液滴胶凝。此溶胶-凝胶方法使氧化铝及氧化硅固定。关于油滴法的其它细节可参见以引用方式并入的美国专利第2,620,314号。
尽管上述方法提供呈球形的非晶形氧化硅-氧化铝组合物,然非晶形氧化硅-氧化铝可呈任何形态(如挤出物、不规则形状颗粒、丸粒或片剂),只要这些对应于成品催化剂的形态。尤其优选使用依上文所述制得的球形物。
连续地从油浴取出这些球形物,及通常使其在油及氨水溶液中接受特定的老化及干燥处理从而获得本发明的催化剂。然后洗涤所得经老化及胶凝的颗粒接着于90℃至150℃的相对低的温度下干燥,并于400℃至700℃的温度下经历煅烧程序历时1至20小时。此提供非晶形氧化硅-氧化铝组合物。这些非晶形氧化硅-氧化铝组合物的特征在于其具有0.3至0.5g/cc的表观松密度及0.4至1.0cc/g的孔体积。
催化剂优选为无粘合剂的,亦即,其包括适用于烃转化方法而实质上不存在能使成品催化剂成形的惰性组分的形式。若存在的话,这些组分是以次要量(例如,以催化剂质量为基础少于50质量%、优选少于10质量%及最优选少于7质量%)存在。任何惰性组分优选包含来自预成形球形物结晶的未转化材料。
无粘合剂型催化剂从由(例如)非晶形或结晶型氧化硅及氧化铝或非晶形氧化硅氧化铝氧化物来源组成的挤出物或球形颗粒制得。还需要矿化剂(如胺、氢氧化钠和/或氟化钠、四烷基铵氢氧化物或溴化物(烷基优选含有2至5个碳原子))和水,以使氧化硅和氧化铝组分转化为无粘合剂型铝硅酸盐沸石颗粒。矿化剂和水可于形成方法期间并入球形颗粒或挤出物中,或它们可在随后作为溶液、多重溶液、蒸汽、蒸气或其任何组合中的任一种添加。亦可少量地添加晶种、成核剂和/或结构导向剂,然一般而言这些并非必要的和/或可避免其的使用。然后所得产物可任选在400至550℃的温度的空气中煅烧10至40小时以移除四烷基铵阳离子。
产物可进一步经处理以移除铝及任选***硅,从而增大Si/Al比及因此改性沸石的酸度及离子交换性能。这些处理包括:a)与氟硅酸盐溶液或浆料接触;b)煅烧或汽蒸,接着再进行酸萃取或离子交换;c)酸萃取或d)这些处理以任意顺序的任何组合。
本发明催化剂的特征为特别高的大孔孔隙度(macroporosity)及高侵入体积,其是依据ASTM D4284标准测试法通过汞侵入测孔法测定催化剂的孔体积分布,其对应于在催化剂中存在中孔及大孔的特征的汞侵入体积。颗粒侵入孔体积一般为至少0.60cc/克,优选至少0.65cc/克及更优选大于0.70cc/克。相较于通过粘结沸石所制得的催化剂,这些特征导致C8-芳族化合物混合物中乙苯的高转化率。
结晶度梯度优选通过扫描电子显微镜(“SEM”)测定。局部结晶度的SEM测定在来自催化剂颗粒床的至少三个样本颗粒上进行。样本是通过本领域技术人员已知的技术从床选择。SEM数据显示基于与相对于颗粒直径的位置相关的结晶度的在催化剂颗粒内任何一点的结晶度。梯度测量值为在至少三个催化剂颗粒内在指定位置处的梯度平均值,且其有用于进行结晶度的相对比较。颗粒结晶度梯度的结晶度比例从具有10至50重量%的结晶度的低结晶度内部至具有90至100重量%的结晶度的高结晶度外部增加;该内部可占颗粒体积的50%。该梯度与在非晶形中心上方具有沸石外层的催化剂形成对照。
图1绘示已经切片来展现本发明梯度的本发明颗粒。颗粒的外部显示高结晶度,而中心部分仅显示一些晶体。朝外部移动观察到结晶比例增大。
本发明的催化剂优选包含金属组分,该组分包括选自第VIII族(IUPAC8-10)、第VIB族(IUPAC6)及第VIIB族(IUPAC7)金属的一种或多种金属。铂族金属中的一种或多种(包括铂、钯、铑、钌、锇及铱中的一种或多种)为本发明催化剂的特别有利的组分。优选的铂族金属为铂及钯,且铂为特别优选。铂族金属组分可作为化合物(如氧化物、硫化物、卤化物、氧硫化物等)存在于最终催化剂复合物中,或作为元素金属或与催化剂复合物中的一种或多种其它成分组合存在于最终催化剂复合物中。认为在实质上所有铂族金属组分以还原态存在时获得最佳结果。铂族金属组分一般占最终催化剂复合物的10至5000质量-ppm(份/1百万份)(基于元素基础计算),以100至2000质量-ppm的含量特别适宜。在使用铂组分的情况下,在催化剂上以元素为基础200至800质量-ppm的铂含量是有利的;且200至500质量-ppm的含量特别有利。
氢化金属组分可以任何适宜方式并入催化剂复合物中。一种制造催化剂的方法涉及使用氢化金属的水溶性可分解化合物来浸渍经煅烧的筛/粘合剂复合物。
于本发明范畴内的催化剂复合物可另外包含金属改性剂,如铼、锡、锗、铅、钴、镍、铟、镓、锌、铀、镝、铊中的一种或多种或其混合物。可通过本领域已知的任何方式将催化有效量的这些金属改性剂并入催化剂中以达成均质或分层分布。
于另一实施方案中,催化剂可包含经分散的选择性硫化铼组分。铼(以元素金属计算)的存在量为催化剂质量的0.05至5、优选0.4至4,及硫对铼的原子比为0.2:1至0.7:1,优选0.25:1至0.5:1。另一催化剂的第一硫化优选使用高度稀释硫化气体,在硫化条件下,使含硫气体通过催化剂之上,例如在现有技术已知的至少0.5hr-1的重量时空间速度及至少100℃的温度下。还原条件可通过在实质上不存在氧化组分的情况下存在烃和氢中的至少一种来提供。硫化气体经常含有小于5000、更优选小于500份/1百万份(以摩尔(ppm-摩尔)计)的硫。
本发明的催化剂可包含卤素组分,包括氟、氯、溴或碘或其混合物,以氯为优选。然而,优选地,催化剂不含除与其它催化剂组分相关联之外的添加卤素。
优选于100℃至320℃的温度下将催化剂复合物干燥2至24小时或更长时间。若需要,可于400℃至650℃的温度在空气氛围中将催化剂煅烧0.1至10小时。亦可于煅烧期间存在蒸汽,例如,以空气为基础为0.5至20,比方说,1至10摩尔%蒸汽。在催化剂包含次要量铂族金属的情况下,所得经煅烧复合物通常经历实质上无水的还原步骤,以确保任选的金属组分均匀及细碎地分散。还原剂在包括200℃至650℃的温度的条件下与催化剂接触0.5至10小时,有效地将(若存在的)实质上所有铂族金属组分还原为金属态。
本发明催化剂的特别优选应用为使C8-芳族混合物中的乙苯有效转化结合了二甲苯异构化。该优选的芳族化合物转化方法的原料包括非平衡二甲苯及乙苯。这些芳族化合物是含于非平衡混合物中,亦即,至少一种C8-芳族异构体是以实质上不同于异构化条件时的平衡浓度的浓度存在。因此,在二甲苯异构体中的一种或两种是相对于其它一种或多种二甲苯异构体以低于平衡比例存在的情况下,呈现非平衡二甲苯组合物。低于平衡比例的二甲苯可为对位-、间位-及邻位-异构体的任何一种。由于对-及邻-二甲苯的需要量大于间-二甲苯的需要量,原料通常将包含间-二甲苯。一般而言该混合物将具有1至60质量%的乙苯含量、0至35质量%的邻-二甲苯含量、20至95质量%的间-二甲苯含量及0至30质量%的对-二甲苯含量。通常,非平衡混合物是通过从获自芳族化合物制备方法的新制C8芳族混合物将对-、邻-和/或间-二甲苯取出而制得。原料可包含其它组分,包括(但不限于)环烷烃及无环链烷烃以及较高及较低分子量的芳族化合物。
烷基芳族烃可作为来自各种不同石油精炼厂料流的适宜馏分中所发现的那些(例如,作为个别组分或经由选择性分馏及蒸馏催化裂化或重组烃所获得的特定沸程馏分)用于本发明中。
根据本发明的方法,在烷基芳族烃转化区中使烷基芳族烃进料混合物(优选与氢混合)与本发明的催化剂接触。可利用固定床***、移动床***、流化床***或分批式操作中的催化剂来实现接触。鉴于贵重催化剂损耗的危险及更简单操作,优选使用固定床***。在该***中,通过适宜加热装置将富氢气体及进料混合物预热至期望的反应温度,然后使其进入含有催化剂固定床的转化区中。转化可在一个或多个单独反应器中实施,在各反应器间具有适宜装置以确保在各区入口处维持期望的转化温度。
反应物可以向上-、向下-或径向-流动方式中的任一种与催化剂床接触,及反应物在与催化剂接触时可呈液相、液-气混合相或蒸气相。这些反应物优选部分或完全地呈蒸气相。
烷基芳族进料混合物(优选为C8芳族化合物的非平衡混合物)在适宜的烷基芳族转化条件下与转化催化剂接触。这些条件包括范围从100℃至600℃或更高及优选在340℃至500℃范围内的温度。压力一般而言为100kPa至10MPa,及更通常不超过5MPa。将足量的催化剂装纳在转化区中,以提供0.5至100hr-1及优选2至50hr-1的针对烃进料混合物的质量时空间速度;在至少10hr-1及更高的质量时空间速度下获得更有利结果。烃进料混合物最佳在混合物中与氢发生反应,氢/烃摩尔比为0.05:1至10:1或更大及优选至少0.05;亦可存有惰性稀释剂,如氮气、氩气及轻质烃。
通常,这些转化条件足以转化进料流中至少50%、优选60至90%的乙苯。本发明方法的特征是从乙苯高度移除乙基且极少形成甲苯及重质烷基苯副产物。一般而言,转化条件不导致达成二甲苯平衡。该转化方法一般而言使乙苯转化,且每%乙苯转化,二甲苯损耗%小于0.025,及优选小于0.02。
在本发明中,烷基芳族烃进料混合物依序在转化区中及接着在随后的二甲苯异构化区中与两种或更多种催化剂接触以达成本发明的目标。此种两催化剂***通过有效的乙苯转化及接着在低乙苯C8芳族化合物混合物中的有效二甲苯异构化而特别有效。可于任一区中使用呈固定床***、移动床***、流化床***、浆料***、沸腾床***或分批式操作的催化剂***来实现接触,但优选在两区中都使用固定床***。第一转化区优选包含在如上所述可有效转化乙苯以及异构化二甲苯的条件下操作的本发明催化剂。该第一转化区生成中间料流,及至少一部分及优选全部中间料流未经进一步处理地在含有异构化催化剂的第二转化区中接触。异构化区可包括单一反应器或两个或更多个独立反应器且其间具有适宜装置以达成改良的到二甲苯平衡的路径。此两种催化剂优选装纳在同一反应器中。
该异构化区优选包含对二甲苯异构化特别有效的催化剂,乙苯已在第一区中转化。可使用有效用于此目的的任何催化剂,包括选自MFI、MEL、EUO、FER、MFS、MTT、MTW、TON、MOR及FAU类型的已知沸石铝硅酸盐,其中pentasil沸石MFI及MTW为优选。反应物可以液相、液-气混合相或蒸气相与第二催化剂接触。操作条件一般是在以上针对本发明催化剂所述的范围内,且在200℃至400℃范围内的较低温度对达成前文所述的较高范围内的对-二甲苯比率为优选。
用以从反应器的流出物回收异构化产物的特定方案不被视为是本发明的关键,及可使用本领域已知的任何有效回收方案。通常,转化产物经分馏以移除轻质副产物(诸如链烷烃、环烷烃、苯及甲苯)及重质副产物而获得C8异构体产物。重质副产物包括二甲基乙基苯及三甲苯。于一些实施例中,可通过选择性分馏从异构化产物回收特定产物物种(如邻-二甲苯或二甲基乙基苯)。来自C8芳族化合物转化的产物通常经处理以选择性地回收对-二甲苯异构体,任选通过结晶。优选是根据US3,201,491使用结晶铝硅酸盐进行选择性吸附。于以引用方式并入本文的US3,626,020、US3,696,107、US4,039,599、US4,184,943、US4,381,419及US4,402,832中说明优选吸附回收法中的改良及替代。
实施例
以下实施例是仅提出用来说明本发明的一些具体实施方案,而不应理解为限制权利要求限定的本发明范围。如本领域技术人员所当明了,在本发明的精神内,存在许多可行的其它变动。
实施例1
本发明第一催化剂的制备如下:在125mL特氟龙(Teflon)内衬中,将11.8克丙胺及4.0克10%NaCl水溶液混合。将8.0克Si/Al2比为80的经煅烧油滴球形物添加至该混合物且被液相完全覆盖。然后将该特氟龙内衬装载于Parr反应器内并加热至175℃维持10天。在冷却至室温之后,过滤出球形物并用去离子水洗涤。依据x射线衍射,这些经煅烧的催化剂颗粒包含70%MFI。通过以含有0.08克氯化四胺铂及9.41克NH4NO3的200毫升水溶液浸渍111克经煅烧产物,接着于100℃下蒸发,产生以成品催化剂颗粒为基础计0.04质量%的最终铂含量来制成催化剂。然后如US7,939,701的实施例1中所述,使浸渍样本经历二阶段煅烧及88℃铵离子交换,接着经历480℃氧化及4-小时425℃还原。该催化剂具有0.718cc/克的ASTM D4284侵入体积及220ppm的铂含量,指示为催化剂A。
实施例2
本发明第二催化剂的制备如下:在125mL特氟龙内衬中,将15克丁胺及10克20%NaCl水溶液混合。将12克Si/Al2为40的经煅烧油滴球形物添加至该混合物且被液相完全覆盖。然后将该特氟龙内衬装载于Parr反应器内并加热至175℃维持10天。在冷却至室温之后,过滤出这些球形物并用DI水洗涤。依据x射线衍射,这些经煅烧的催化剂颗粒包含50%MFI。通过以含有0.08克氯化四胺铂及9.41克NH4NO3的200毫升水溶液浸渍111克经煅烧产物,接着于100℃下蒸发,产生以成品催化剂颗粒为基础计0.04质量%的最终铂含量来制成催化剂。然后如美国专利案第7,939,701号的实施例1中所述使浸渍样本经历二阶段煅烧及88℃铵离子交换,接着经历480℃氧化及4-小时425℃还原。该催化剂具有0.743cc/克的ASTM D4284侵入体积及350ppm的铂含量,指示为催化剂B。
实施例3
将本发明催化剂的性能与依据美国专利案第7,939,701号的实施例2制得的已知技术的参考催化剂作比较。通过使实质上不存在对-二甲苯且含有15质量%乙苯、25质量%邻-二甲苯及60质量%间-二甲苯的进料流异构化来进行各试验。这些试验是在氢对烃比率为4比1、重量时空间速度为7,且压力为0.7MPa表压下实施。在375℃至400℃范围内的测试温度下达成70%的乙苯转化率。测量二甲苯的损耗及副产物甲苯及重质烷基苯的伴随产量作为性能如下:
催化剂 | A | B | 参考值 |
温度,℃ | 375 | 388 | 371 |
对-二甲苯/总二甲苯,% | 16 | 6 | 24 |
二甲苯损耗,% | 1.1 | 0.4 | 1.9 |
甲苯+重质副产物,质量% | 09 | 03 | 17 |
本发明的两催化剂当转化乙苯时展现较参考催化剂低的二甲苯损耗及副产物产率,且提高产物中对-二甲苯的比例。应注意二甲苯损耗对乙苯转化率的比率分别为0.016、0.006及0.027。
Claims (9)
1.一种用于转化非平衡C8-芳族原料的方法,该方法包括使该原料与包含非结合沸石铝硅酸盐颗粒的催化剂床接触,所述颗粒具有至少0.65cc/克的颗粒侵入孔体积及结晶度比例从低结晶度内部增加至高结晶度外部的颗粒结晶度梯度,该接触在转化区中以包括340℃至500℃的温度、100kPa至5MPa的压力及2至50hr-1的质量时空间速度的转化条件在氢存在下进行,以使乙苯转化,其中二甲苯损耗低且获得异构化产物,该异构化产物含有比在该原料中更高比例的至少一种二甲苯异构体。
2.如权利要求1的方法,其中该颗粒侵入孔体积为至少0.7cc/克。
3.如权利要求1的方法,其中该催化剂颗粒的内部定义为对应于经颗粒半径的一半包围的体积的颗粒部分。
4.如权利要求1的方法,其中该催化剂颗粒的该内部定义为该催化剂颗粒的内部50%的体积。
5.如权利要求3或4的方法,其中该催化剂颗粒的该内部的该相对结晶度为10至50%。
6.如权利要求3或4的方法,其中该催化剂颗粒的该外部的该相对结晶度为90至100%。
7.如权利要求1或2的方法,其中该催化剂具有球形构形。
8.如权利要求7的方法,其中该催化剂的该球形构形包括油滴的特征。
9.如权利要求1或2的方法,其中每%乙苯转化,二甲苯损耗%小于0.02%。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/286,553 US8889940B2 (en) | 2011-11-01 | 2011-11-01 | Catalyst and process for hydrocarbon conversion |
US13/286,553 | 2011-11-01 | ||
PCT/US2012/056178 WO2013066509A1 (en) | 2011-11-01 | 2012-09-20 | Catalyst and process for hydrocarbon conversion |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103842318A true CN103842318A (zh) | 2014-06-04 |
CN103842318B CN103842318B (zh) | 2015-09-02 |
Family
ID=48173066
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201280049036.8A Active CN103842318B (zh) | 2011-11-01 | 2012-09-20 | 用于烃转化的催化剂及方法 |
Country Status (12)
Country | Link |
---|---|
US (1) | US8889940B2 (zh) |
EP (1) | EP2773603B1 (zh) |
JP (1) | JP5908598B2 (zh) |
KR (1) | KR101615462B1 (zh) |
CN (1) | CN103842318B (zh) |
BR (1) | BR112014007979A2 (zh) |
HU (1) | HUE035680T2 (zh) |
PL (1) | PL2773603T3 (zh) |
RU (1) | RU2570427C1 (zh) |
SG (1) | SG11201401173QA (zh) |
TW (1) | TWI461241B (zh) |
WO (1) | WO2013066509A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108349836A (zh) * | 2015-10-28 | 2018-07-31 | Bp北美公司 | 用于二甲苯异构化方法中乙基苯转化的改进催化剂 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9688587B2 (en) | 2015-03-03 | 2017-06-27 | Uop Llc | Process for oxygenate to olefin conversion using 2-D pentasil zeolite |
US9890094B2 (en) | 2015-03-03 | 2018-02-13 | Uop Llc | High meso-surface area and high acid site density pentasil zeolite for use in xylene conversion |
US10010878B2 (en) | 2015-03-03 | 2018-07-03 | Uop Llc | High meso-surface area, low Si/Al ratio pentasil zeolite |
US9643897B2 (en) | 2015-03-03 | 2017-05-09 | Uop Llc | Enhanced propylene production in OTO process with modified zeolites |
US10336665B2 (en) | 2015-03-03 | 2019-07-02 | Uop Llc | Yields in xylene isomerization using layer MFI zeolites |
US11229899B2 (en) | 2016-12-09 | 2022-01-25 | Shell Oil Company | Catalyst composition |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3909450A (en) * | 1973-12-26 | 1975-09-30 | Universal Oil Prod Co | Method of catalyst manufacture |
CN1170396A (zh) * | 1994-11-23 | 1998-01-14 | 埃克森化学专利公司 | 应用沸石结合沸石催化剂的烃转化过程 |
CN1342631A (zh) * | 2000-09-08 | 2002-04-03 | 环球油品公司 | 选择性二甲苯异构化和乙苯转化 |
US20110245565A1 (en) * | 2010-03-31 | 2011-10-06 | Uop Llc | Process for Xylene and Ethylbenzene Isomerization Using UZM-35 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL76445C (zh) | 1950-03-08 | |||
US3201491A (en) | 1962-09-05 | 1965-08-17 | Universal Oil Prod Co | Continuous sorption process with emphasis on product purity |
US3626020A (en) | 1969-03-12 | 1971-12-07 | Universal Oil Prod Co | Separation of paraxylene from mixture of c aromatic utilizing crystalline aluminosilicate adsorbent |
US3696107A (en) | 1971-05-27 | 1972-10-03 | Richard W Neuzil | Improved hydrocarbon separation process |
US4039599A (en) | 1976-08-26 | 1977-08-02 | Uop Inc. | Xylene isomerization process |
US4184943A (en) | 1978-12-21 | 1980-01-22 | Uop Inc. | Fractionation in an adsorptive hydrocarbon separation process |
US4381419A (en) | 1981-04-22 | 1983-04-26 | Exxon Research & Engineering Co. | Adsorption-desorption separation process with integrated light and heavy desorbents |
US4402832A (en) | 1982-08-12 | 1983-09-06 | Uop Inc. | High efficiency continuous separation process |
US4864068A (en) | 1987-06-04 | 1989-09-05 | Uop | Oligomerization processes and catalysts |
DE4042655C2 (de) * | 1990-07-11 | 1996-12-19 | Ecolith Zeolithe Gmbh | Verwendung eines synthetischen, kristallinen Alumosilikats mit der chemischen Zusammensetzung 0-3M¶2¶O : Al¶2¶O¶3¶ : 15-40SiO¶2¶ : 0-40H¶2¶O zur Gewinnung und Verarbeitung von Aromaten |
GB9101456D0 (en) | 1991-01-23 | 1991-03-06 | Exxon Chemical Patents Inc | Process for producing substantially binder-free zeolite |
CA2174045C (en) * | 1995-04-24 | 2003-01-28 | John Ivor Hammerman | C8 aromatics isomerization using catalyst containing modified silicoaluminophosphate molecular sieve |
BR0011275A (pt) | 1999-05-20 | 2002-02-26 | Exxonmobil Chem Patents Inc | Processo de conversão de hidrocarbono e catalisadores úteis a esse respeito |
RU2233260C2 (ru) | 2000-09-13 | 2004-07-27 | Юоп Ллк | Селективная изомеризация ксилолов и конверсия этилбензола |
US7638459B2 (en) | 2005-05-25 | 2009-12-29 | Uop Llc | Layered composition and processes for preparing and using the composition |
US7297830B2 (en) * | 2005-09-14 | 2007-11-20 | Uop Llc | Process for isomerizing non-equilibrium xylene-containing feed streams |
TWI478768B (zh) | 2007-07-18 | 2015-04-01 | China Petro Chemical Technologydevelopment Company | Catalysts and methods for the production of light aromatics and light alkanes from hydrocarbon feedstocks |
US7812205B2 (en) | 2007-10-12 | 2010-10-12 | Uop Llc | Layered zeolitic catalyst for improved linearity in detergent alkylation |
US7939701B2 (en) * | 2007-12-12 | 2011-05-10 | Uop Llc | Aromatic isomerization catalyst and a process of use thereof |
US20130064757A1 (en) * | 2011-09-09 | 2013-03-14 | Uop Llc | Methods for forming zeolites from homogeneous amorphous silica alumina |
-
2011
- 2011-11-01 US US13/286,553 patent/US8889940B2/en active Active
-
2012
- 2012-09-20 SG SG11201401173QA patent/SG11201401173QA/en unknown
- 2012-09-20 EP EP12846661.2A patent/EP2773603B1/en not_active Not-in-force
- 2012-09-20 WO PCT/US2012/056178 patent/WO2013066509A1/en active Application Filing
- 2012-09-20 PL PL12846661T patent/PL2773603T3/pl unknown
- 2012-09-20 KR KR1020147008606A patent/KR101615462B1/ko active IP Right Grant
- 2012-09-20 CN CN201280049036.8A patent/CN103842318B/zh active Active
- 2012-09-20 BR BR112014007979A patent/BR112014007979A2/pt not_active IP Right Cessation
- 2012-09-20 RU RU2014113066/04A patent/RU2570427C1/ru not_active IP Right Cessation
- 2012-09-20 JP JP2014539952A patent/JP5908598B2/ja active Active
- 2012-09-20 HU HUE12846661A patent/HUE035680T2/en unknown
- 2012-10-11 TW TW101137540A patent/TWI461241B/zh not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3909450A (en) * | 1973-12-26 | 1975-09-30 | Universal Oil Prod Co | Method of catalyst manufacture |
CN1170396A (zh) * | 1994-11-23 | 1998-01-14 | 埃克森化学专利公司 | 应用沸石结合沸石催化剂的烃转化过程 |
CN1342631A (zh) * | 2000-09-08 | 2002-04-03 | 环球油品公司 | 选择性二甲苯异构化和乙苯转化 |
US20110245565A1 (en) * | 2010-03-31 | 2011-10-06 | Uop Llc | Process for Xylene and Ethylbenzene Isomerization Using UZM-35 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108349836A (zh) * | 2015-10-28 | 2018-07-31 | Bp北美公司 | 用于二甲苯异构化方法中乙基苯转化的改进催化剂 |
CN108349836B (zh) * | 2015-10-28 | 2021-04-20 | Bp北美公司 | 用于二甲苯异构化方法中乙基苯转化的改进催化剂 |
Also Published As
Publication number | Publication date |
---|---|
KR20140070577A (ko) | 2014-06-10 |
TW201325718A (zh) | 2013-07-01 |
CN103842318B (zh) | 2015-09-02 |
PL2773603T3 (pl) | 2017-10-31 |
RU2570427C1 (ru) | 2015-12-10 |
EP2773603A4 (en) | 2015-12-02 |
EP2773603A1 (en) | 2014-09-10 |
KR101615462B1 (ko) | 2016-04-25 |
EP2773603B1 (en) | 2017-05-17 |
US20130109899A1 (en) | 2013-05-02 |
WO2013066509A1 (en) | 2013-05-10 |
US8889940B2 (en) | 2014-11-18 |
HUE035680T2 (en) | 2018-05-28 |
TWI461241B (zh) | 2014-11-21 |
JP2015502342A (ja) | 2015-01-22 |
JP5908598B2 (ja) | 2016-04-26 |
SG11201401173QA (en) | 2014-08-28 |
BR112014007979A2 (pt) | 2017-04-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103842318B (zh) | 用于烃转化的催化剂及方法 | |
JP3347752B2 (ja) | ゼオライト | |
US8629073B2 (en) | Catalyst comprising an izm-2 zeolite and at least one metal, and its use in the transformation of hydrocarbons | |
KR101519409B1 (ko) | Zsm-5, 이의 제조 및 에틸벤젠 탈알킬화에서의 이의 용도 | |
EP2931686B1 (en) | Aromatic transalkylation using uzm-44 aluminosilicate zeolite | |
KR101790368B1 (ko) | 단환 방향족 탄화수소 제조용 촉매 및 단환 방향족 탄화수소의 제조 방법 | |
KR20100041857A (ko) | 촉매 조성물, 이의 제조법 및 이의 용도 | |
NO303677B1 (no) | Zeolitt-katalysator, fremgangsmÕte for fremstilling derav og fremgangsmÕte for anvendelse derav | |
JP2000143235A (ja) | 構造化剤の前駆体を用いるeuo構造型ゼオライトの調製方法およびc8芳香族化合物の異性化触媒としてのその使用 | |
EP2794525B1 (en) | Aromatic transformation using uzm-39 aluminosilicate zeolite | |
WO2011075925A1 (zh) | 一种小晶粒稀土-zsm5/zsm11共结晶沸石的合成方法 | |
US20110201860A1 (en) | Process for conversion of alkanes to aromatics | |
US8716540B1 (en) | Aromatic transformation using UZM-44 aluminosilicate zeolite | |
EA001597B1 (ru) | Способ изомеризации алкилароматических углеводородов | |
WO2009016141A1 (en) | Catalyst composition, its preparation and use | |
JP2014024007A (ja) | ゼオライト触媒、ゼオライト触媒の製造方法および低級オレフィンの製造方法 | |
KR20190023054A (ko) | Zsm-5-계 촉매 제조; 에틸벤젠 탈알킬화 공정에서의 용도 | |
EP2260000A2 (en) | High metal content molecular sieves and their manufacture | |
CN100384732C (zh) | 合成小晶粒β沸石的方法 | |
CN100384731C (zh) | 制备小晶粒β沸石的方法 | |
SG188173A1 (en) | Large crystal molecular sieves and their manufacture | |
JP6251788B2 (ja) | ゼオライト触媒、ゼオライト触媒の製造方法および低級オレフィンの製造方法 | |
US20220410131A1 (en) | Alkylaromatic conversion catalyst system | |
CN103930389A (zh) | 使用双催化剂***的芳香族化合物异构化 | |
CN114829006A (zh) | 催化剂及其在乙苯脱烷基化中的用途 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |