TWI461241B - 用於烴轉換之觸媒及方法 - Google Patents
用於烴轉換之觸媒及方法 Download PDFInfo
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- TWI461241B TWI461241B TW101137540A TW101137540A TWI461241B TW I461241 B TWI461241 B TW I461241B TW 101137540 A TW101137540 A TW 101137540A TW 101137540 A TW101137540 A TW 101137540A TW I461241 B TWI461241 B TW I461241B
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- Taiwan
- Prior art keywords
- catalyst
- xylene
- particles
- crystallinity
- conversion
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 92
- 238000000034 method Methods 0.000 title claims description 45
- 238000006243 chemical reaction Methods 0.000 title claims description 41
- 229930195733 hydrocarbon Natural products 0.000 title description 15
- 150000002430 hydrocarbons Chemical class 0.000 title description 15
- 239000004215 Carbon black (E152) Substances 0.000 title description 11
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 64
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 37
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 30
- 239000010457 zeolite Substances 0.000 claims description 29
- 239000008096 xylene Substances 0.000 claims description 27
- 229910021536 Zeolite Inorganic materials 0.000 claims description 24
- 238000006317 isomerization reaction Methods 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 3
- 238000002459 porosimetry Methods 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims 1
- 150000003613 toluenes Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 23
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 17
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 150000003738 xylenes Chemical class 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 10
- -1 aluminum alkoxides Chemical class 0.000 description 10
- 229910000420 cerium oxide Inorganic materials 0.000 description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- 229910000323 aluminium silicate Inorganic materials 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
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- 239000002131 composite material Substances 0.000 description 5
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- 238000011084 recovery Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
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- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
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- 238000005342 ion exchange Methods 0.000 description 4
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- 229940078552 o-xylene Drugs 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000000243 solution Substances 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
- 238000011282 treatment Methods 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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-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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 230000000694 effects 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
- 238000005194 fractionation Methods 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-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
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- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 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
- 238000004073 vulcanization Methods 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-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
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 229910052776 Thorium Inorganic materials 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
- DUDJJJCZFBPZKW-UHFFFAOYSA-N [Ru]=S Chemical compound [Ru]=S DUDJJJCZFBPZKW-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 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
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 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
- 230000005587 bubbling Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 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
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 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
- 239000012084 conversion product Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 210000003298 dental enamel Anatomy 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002552 dosage form Substances 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
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- 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
- 238000001879 gelation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 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
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-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
- 239000011133 lead Substances 0.000 description 1
- 230000002535 lyotropic effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 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
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002407 reforming 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
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 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
- 239000011973 solid acid Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide 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
- 238000012546 transfer 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
- 239000002023 wood Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—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
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Description
本發明係關於用於烴轉換之觸媒及方法。更特定言之,本發明揭示用於有效轉換乙苯及異構化二甲苯之觸媒。
本申請案主張2011年11月1日申請之美國申請案第13/286,553號之優先權。
沸石被廣泛地作為觸媒用於多種類型之烴轉換過程,諸如異構化、重整、氫化、烷基化、轉烷化、裂化及加氫裂化。另外,沸石材料被作為吸附劑用於多種石油及化學品分離過程。催化或分離作用之選擇性係由結晶鋁矽酸鹽網絡所形成的間隙空間或通道所賦予。沸石亦可包括其中已完全或部分地以其他氧化物取代氧化矽及氧化鋁部分之材料;氧化鍺、氧化錫及其混合物可取代氧化矽部分及氧化鎵、氧化銦、氧化硼、氧化鐵及其混合物可取代氧化鋁部分。
純沸石之實際應用因機械強度限制而嚴格受限。機械強度可藉由在非沸石黏結劑存在下形成沸石然後乾燥繼而煅燒所得擠出丸粒、球或擠出物而賦予。該等黏結劑之實例包括諸如氧化鋁、氧化矽、鈦及不同類型黏土之材料。然而,因為黏結劑會減弱沸石之吸附性質,故結合沸石就活性、選擇性或活性維持而言之有效性可能減低。另外,由於結合沸石係藉由使沸石與黏結劑一起擠出接著乾燥繼而煅燒該擠出物而製備,故非晶型黏結劑可滲入沸石的孔
隙,或者阻塞該等沸石孔隙之進口,或減慢轉移至該等沸石孔隙之質量轉移速率,此等可減低沸石之有效性。再者,當將結合沸石用於催化過程時,黏結劑會影響在沸石中發生之化學反應及亦可能催化不期望的反應而可能導致形成非所欲產物。
沸石觸媒之主要應用係轉換C8
芳族烴以獲得個別二甲苯異構體。二甲苯、對二甲苯、間二甲苯及鄰二甲苯為在化學合成中具有寬廣及多種應用之重要中間物。對二甲苯在氧化時生成用於製造合成織物纖維及樹脂之對苯二甲酸。間二甲苯係用於製造塑化劑、偶氮染料、木材防腐劑等。鄰二甲苯為用於製造苯二甲酸酐之原料。
石油石腦油之催化重整係C8
芳族烴之重要來源。來自催化重整或其他來源之C8
芳族烴中之二甲苯異構體一般不匹配作為化學中間物之需求比例,且進一步包括難以分離或轉換之乙苯。對二甲苯特定言之為其需求快速增長的主要化學中間物,但其量僅佔典型C8
芳族烴流的15至20%。調整異構體比率以達需求可藉由組合二甲苯異構體回收(諸如針對對二甲苯回收之吸附)與異構化以產生額外量之期望異構體來實現。異構化使所期望二甲苯異構體貧乏之二甲苯異構體之非平衡混合物轉換為接近平衡濃度之混合物。所利用之接近平衡係高轉換率(即,極其接近平衡)時之高C8
環狀化物損耗與由未經轉換之C8
芳族烴之大再循環速率所致之高公用事業成本之間之最佳折衷。
用於轉換C8
芳族烴之方法通常係以轉換與二甲苯異構體
相關聯之乙苯的方式分類。乙苯不易異構化為二甲苯,但其通常在製程單元中轉換,因為藉由超分餾或吸附將其自二甲苯分離的成本極高。一種方法係藉由在具有氫化-脫氫功能之固體酸催化劑存在下轉換成環烷烴及自環烷烴再轉換而使乙苯反應形成二甲苯混合物。另一種廣泛採用的方法係使乙苯脫烷基以主要形成苯,同時使二甲苯異構化為近平衡混合物。前一方法藉由自乙苯形成二甲苯從而提高二甲苯產率;後一方法通常達成較高的乙苯轉換率,因而降低再循環至對二甲苯回收單元之量及減低附隨的處理成本。
氫一般存於轉換製程反應物中以促進反應及維持觸媒穩定性。雖然二甲苯於一些情況下可在無氫存在下異構化從而節省費用,但乙苯轉換通常需要存在氫。於一些情況中兩階段處理單元可經證實對達成高轉換率及乙苯產率合用。無論如何,仍繼續尋找更有效的觸媒及方法。
本發明之主要目標係提供一種可有效用於轉換烴之新穎觸媒。更特定言之,本發明包括一種用於轉換烷基芳族烴及特定言之用於處理C8
芳族烴以增加期望二甲苯異構體之濃度且降低芳族烴損耗及降低處理成本之方法。
本發明係以可藉由包含具有特定孔隙度及結晶度梯度特徵之無黏結劑沸石之觸媒達成與二甲苯異構化相關聯之乙苯轉換之發現為基礎。
因此,本發明之一實施例係一種用於轉換非平衡C8
-芳
族烴原料之方法,該方法包括使原料與包含非結合沸石鋁矽酸鹽顆粒之觸媒床接觸,該等顆粒具有至少0.65 cc/公克之顆粒侵入孔隙體積及結晶度比例自低結晶度內部至高結晶度外部增加之顆粒結晶度梯度,該接觸係於轉換區中以包括340℃至500℃之溫度、100 kPa至5 MPa之壓力及2至50 hr-1
之質量每小時空間速度之轉換條件在氫存在下進行,以使乙苯轉換及獲得異構化產物,該產物含有較在原料中更高比例之至少一種二甲苯異構體。
一更特定實施例係一種用於轉換非平衡C8
-芳族烴原料之方法,該方法包括使原料與包含非結合沸石鋁矽酸鹽顆粒之觸媒床接觸,該等顆粒具有至少0.65 cc/公克之顆粒侵入孔隙體積及結晶度比例自具有10至50重量%之相對結晶度之內部增加至具有90至100重量%之相對結晶度之高結晶度500微米外部之顆粒結晶度梯度,該接觸係於轉換區中以包括340℃至500℃之溫度、100 kPa至5 MPa之壓力及2至50 hr-1
之質量每小時空間速度之轉換條件在氫存在下進行,以使乙苯轉換及獲得異構化產物,該產物含有較在原料中更高比例之至少一種二甲苯異構體。
又一更特定實施例係一種用於轉換非平衡C8
-芳族烴原料之方法,該方法包括使原料與包含非結合沸石鋁矽酸鹽顆粒之觸媒床接觸,該等顆粒具有至少0.65 cc/公克之顆粒侵入孔隙體積及結晶度比例自具有10至50重量%之相對結晶度之內部增加至具有90至100重量%之相對結晶度之高結晶度100微米外部之顆粒結晶度梯度,該接觸係於轉
換區中以包括340℃至500℃之溫度、100 kPa至5 MPa之壓力及2至50 hr-1
之質量每小時空間速度之轉換條件在氫存在下進行,以使乙苯轉換,且每%乙苯轉換,二甲苯損耗小於0.02,及獲得異構化產物,該產物含有較原料中更高比例之至少一種二甲苯異構體。
可自本發明之以下詳細論述明瞭其他特定實施例。
本發明之無黏結劑球形沸石顆粒之特徵為針對烴轉換及尤其係針對芳族烴轉換之高催化活性及選擇性。本發明含沸石觸媒之實例包括彼等具有Si:Al2
比大於10及通常大於20者,諸如MFI、MEL、EUO、FER、MFS、MTT、MTW、TON、MOR及FAU類型之沸石作為骨架類型者,如Atlas of Zeolite Framework Types
,修改版第6版,C.H.Baerlocher、L.B.McCusker及D.H.Olson編輯,Elsevier(2007)中所述。諸如MFI、MEL、MTW及TON之Pentasil沸石為較佳,及諸如ZSM-5、矽質岩、Borolite C、TS-1、ZSM-12、SSZ-25、PSH-3及ITQ-1之MFI型沸石為特佳。
製備本發明之較佳觸媒首先包括形成鋁及矽之反應混合物。鋁之來源包括(但不限於)鋁烷氧化物、沉澱氧化鋁、鋁金屬、鋁鹽及氧化鋁溶膠。鋁烷氧化物之特定實例包括(但不限於)第二丁醇鋁及鄰異丙醇鋁。氧化矽之來源包括(但不限於)正矽酸四乙酯、膠態二氧化矽、沉澱二氧化矽、鹼性矽酸鹽、HiSil及Ultrasil。Si/Al比可為3至100,及較佳為8至50。
較佳地,氧化矽-氧化鋁混合物實質上不含如上文所述之沸石或如下文所述之結構導向劑,然而,於本發明之範疇內,該等物質可相對少量地存在。
一種較佳方法包括藉由相關技藝所熟知方法製造非晶型氧化矽-氧化鋁。例如,可使用闡述於以引用方式併入之US 3,909,450中之程序。該程序涉及在回流溫度下於鹽酸水溶液中蒸煮鋁以製備鋁溶膠,從而形成具有預定鋁/氯化物比之溶膠。將該鋁溶膠與已(例如)藉由酸化水玻璃製得之矽溶膠混合。添加諸如六亞甲基四胺、尿素或其混合物之膠凝劑及溶膠混合物呈液滴分散在其中發生膠凝化伴隨形成球形顆粒之熱油浴中。膠凝劑使溶膠液滴之pH提高,致使該等液滴膠凝。此溶凝膠過程使氧化鋁及氧化矽固定。關於油滴法之其他細節可參見以引用方式併入之美國專利案第2,620,314號。
儘管上述程序提供呈球形的非晶型氧化矽-氧化鋁組合物,然非晶型氧化矽-氧化鋁可呈諸如擠出物、不規則形狀顆粒、丸粒或錠之任何形態,只要其等各自對應於完成觸媒之形態。尤佳使用依上文所述製得之球形物。
不間斷地自油浴取出該等球形物,及通常使其於油及氨水溶液中接受特定的熟化及乾燥處理從而獲致本發明之觸媒。然後洗滌所得經熟化及膠凝之顆粒接著於90℃至150℃之相對低的溫度下乾燥,繼而於400℃至700℃之溫度下經歷煅燒程序歷時1至20小時。此提供非晶型氧化矽-氧化鋁組合物。此等非晶型氧化矽-氧化鋁組合物之特徵
在於其等具有0.3至0.5 g/cc之表觀鬆密度及0.4至1.0 cc/g之孔隙體積。
觸媒較佳為無黏結劑型,亦即,其包括適用於烴轉換過程而實質上不存有能使成品觸媒成形之惰性組份之形態。若存在的話,該等組份係以少量(例如,以觸媒質量計50質量%以下、較佳10質量%以下及最佳7質量%以下)存在。任何惰性組份較佳包含使預成形球形物結晶而得的未轉換物質。
無黏結劑型觸媒係自由(例如)非晶型或結晶型氧化矽及氧化鋁或非晶型氧化矽氧化鋁氧化物來源組成之擠出物或球形顆粒製得。亦需要諸如胺、氫氧化鈉及/或氟化鈉、四烷基銨氫氧化物或溴化物(該等烷基較佳含有2至5個碳原子)之礦化劑及水,以使該等氧化矽及氧化鋁組份轉換為無黏結劑型鋁矽酸鹽沸石顆粒。礦化劑及水可於形成過程期間併入球形顆粒或擠出物中,或其等可在隨後作為溶液、多種溶液、蒸汽、蒸氣或其任何組合中之任一者添加。亦可少量地添加晶種、成核劑及/或結構導向劑,然一般而言此等並非必要的及/或可避免其之使用。然後所得產物可視需要在400至550℃之溫度的空氣中煅燒10至40小時以移除四烷基銨陽離子。
產物可進一步經處理以移除鋁及視情況插入矽,因而增大Si/Al比及因此改良沸石之酸度及離子交換性能。該等處理包括:a)與氟矽酸鹽溶液或漿液接觸;b)煅燒或汽蒸,接著再進行酸萃取或離子交換;c)酸萃取或d)該等處理以
任意順序之任何組合。
本發明觸媒之特徵為特別高的大孔隙度及高侵入體積,其等係依據ASTM D4284標準測試法藉由汞侵入測孔法測定觸媒之孔隙體積分佈,其對應於在觸媒中存在中孔及大孔隙之特徵的汞侵入體積。顆粒侵入孔隙體積一般為至少0.60 cc/公克,較佳至少0.65 cc/公克及更佳大於0.70 cc/公克。相較於藉由黏結沸石所製得之觸媒,該等特徵導致C8
-芳族烴混合物中乙苯之高轉換率。
結晶度梯度較佳係藉由掃描電子顯微鏡(「SEM」)測定。局部結晶度之SEM測定係於來自觸媒顆粒床之至少三個樣本顆粒上進行。樣本係藉由熟習相關技藝者所熟知之技術自床選擇。SEM資料顯示基於與相對於顆粒直徑之位置相關之結晶度之在觸媒顆粒內任何一點之結晶度。梯度測量值為在至少三個觸媒顆粒內在指定位置處之梯度平均值,及其有用於進行結晶度之相對比較。顆粒結晶度梯度之結晶度比例自具有10至50重量%之結晶度之低結晶度內部至具有90至100重量%之結晶度之高結晶度外部增加;該內部可佔顆粒體積之50%。該梯度與具有在非晶型中心上方之沸石外層的觸媒形成對照。
圖1繪示已經切片來展現本發明梯度之本發明顆粒。顆粒之外部顯示高結晶度,而中心部分僅顯示一些晶體。朝外部移動觀察到結晶比例增大。
本發明之觸媒較佳包含金屬組份,該組份包括選自第VIII族(IUPAC 8-10)、第VIB族(IUPAC 6)及第VIIB族
(IUPAC 7)金屬之一或多種金屬。鉑族金屬中之一或多者(包括鉑、鈀、銠、釕、鋨及銥中之一或多者)為本發明觸媒之特別有利的組份。較佳之鉑族金屬為鉑及鈀,且鉑為特別佳。鉑族金屬組份可呈諸如氧化物、硫化物、鹵化物、氧硫化物等之化合物或呈元素金屬或以與觸媒複合物中之一或多種其他成分組合形式存於最終觸媒複合物中。咸信在實質上所有鉑族金屬組份以還原態存在時獲得最佳結果。鉑族金屬組份一般佔最終觸媒複合物之10至5000質量-ppm(份/1百萬份)(基於元素計算),以100至2000質量-ppm之含量特別適宜。在使用鉑組份之情況下,含量在200至800質量-ppm之基於元素基礎載於觸媒之鉑係有利的;且200至500質量-ppm之含量特別有利。
氫化金屬組份可以任何適宜方式併入觸媒複合物中。一種製造觸媒之方法涉及使用氫化金屬之水溶性可分解化合物來浸漬經煅燒之篩/黏結劑複合物。
於本發明範疇內之觸媒複合物可另外包含金屬改質劑,諸如錸、錫、鍺、鉛、鈷、鎳、銦、鎵、鋅、鈾、鏑、鉈中之一或多者或其混合物。可藉由相關技藝已知之任何方式將催化有效量之該等金屬改質劑併入觸媒中以達成均質或分層分佈。
於另一實施例中,觸媒可包含經分散之選擇性硫化錸組份。錸(以元素金屬計算)之存在量為觸媒質量之0.05至5、較佳0.4至4,及硫對錸之原子比為0.2:1至0.7:1,較佳0.25:1至0.5:1。另一觸媒之第一硫化較佳係使用高度稀釋
硫化氣體,在硫化條件下,例如,於相關技藝已知之至少0.5 hr-1
之重量每小時空間速度及至少100℃之溫度下,使含硫氣體通過觸媒之上。還原條件可藉由在實質上不存在氧化組份之情況下存在烴及氫中之至少一者來提供。硫化氣體經常含有小於5000、更佳小於500份/1百萬份(以莫耳(ppm-莫耳)計)之硫。
本發明之觸媒可包含鹵素組份,包括氟、氯、溴或碘或其混合物,以氯為較佳。然而,較佳地,觸媒不含除與其他觸媒組份相關聯者外之添加鹵素。
較佳於100℃至320℃之溫度下將觸媒複合物乾燥2至24小時或更長時間。若需要,可於400℃至650℃之溫度之空氣氛圍中將觸媒煅燒0.1至10小時。亦可於煅燒期間存在蒸汽,例如,以空氣計為0.5至20,比方說,1至10莫耳%蒸汽。在觸媒包含少量鉑族金屬之情況下,所得經煅燒複合物通常經歷實質上無水的還原步驟,以確保選用金屬組份均勻及細切地分散。還原劑於包括200℃至650℃之溫度之條件下與觸媒接觸且維持0.5至10小時,其可有效地將若存在的實質上所有鉑族金屬組份還原為金屬態。
本發明觸媒之特佳應用為使C8
-芳族混合物中之乙苯有效轉換以及使二甲苯異構化。該較佳芳族烴轉換過程之原料包括非平衡二甲苯及乙苯。該等芳族化合物係含於非平衡混合物中,亦即,至少一種C8
-芳族異構體係以實質上不同於異構化條件時之平衡濃度的濃度存在。因此,在二甲苯異構體中之一或兩者係相對於其他一或多種二甲苯異
構體以低於平衡比例存在之情況下,呈現非平衡二甲苯組合物。低於平衡比例之二甲苯可為對位-、間位-及鄰位-異構體之任何一者。由於對-及鄰-二甲苯之需要量大於間-二甲苯之需要量,因此原料通常將包含間-二甲苯。一般而言該混合物將具有1至60質量%之乙苯含量、0至35質量%之鄰-二甲苯含量、20至95質量%之間-二甲苯含量及0至30質量%之對-二甲苯含量。通常,非平衡混合物係藉由自獲自芳族烴製程之新製C8
芳族混合物將對-、鄰-及/或間-二甲苯移除來製得。原料可包含其他組份,包括(但不限於)環烷烴及非環狀石蠟以及較高及較低分子量之芳族烴。
烷基芳族烴可呈如來自各種不同石油精煉廠物流之適宜餾份中所見者,例如,呈個別組份或經由選擇性分餾及蒸餾催化裂化或重組烴所獲得之特定沸騰範圍餾份,用於本發明中。
根據本發明之方法,在烷基芳族烴轉換區中使較佳與氫呈混合物形式之烷基芳族烴進料混合物與本發明之觸媒接觸。可利用存於固定床系統、移動床系統、流化床系統或分批式操作中之觸媒來實現接觸。鑑於貴重觸媒損耗之危險及較簡單操作,最好使用固定床系統。於該系統中,藉由適宜加熱構件將富氫氣體及進料混合物預熱至期望反應溫度,然後使其進入含有固定觸媒床之轉換區中。轉換可於一或多個個別反應器中實施,在各反應器間具有適宜構件以確保在各區入口處維持期望的轉換溫度。
反應物可以向上-、向下-或徑向-流動方式中之任一者與
觸媒床接觸,及反應物在與觸媒接觸時可呈液相、液-氣混合相或氣相。該等反應物較佳部分或完全地呈氣相。
較佳為C8
芳族烴之非平衡混合物之烷基芳族進料混合物於適宜之烷基芳族烴轉換條件下與轉換觸媒接觸。該等條件包括範圍自100℃至600℃或更高及較佳在340℃至500℃範圍內之溫度。壓力一般而言為100 kPa至10 MPa,及更通常不超過5 MPa。將足量的觸媒裝納在轉換區中,以提供0.5至100 hr-1
及較佳2至50 hr-1
之相對於烴進料混合物之質量每小時空間速度;於至少10 hr-1
及更高的質量每小時空間速度下獲得有利結果。烴進料混合物最佳在混合物中與氫發生反應,氫/烴莫耳比為0.05:1至10:1或更大及較佳至少0.05;亦可存有諸如氮氣、氬氣及輕質烴之惰性稀釋劑。
通常,該等轉換條件足以轉換進料流中至少50%、較佳60至90%之乙苯。本發明方法之特徵係自乙苯高度移除乙基且極少形成甲苯及重質烷基苯副產物。一般而言,該等轉換條件不會導致達成二甲苯平衡。該轉換過程一般而言使乙苯轉換,且每%乙苯轉換,二甲苯損耗%小於0.025,及較佳小於0.02。
於本發明中,烷基芳族烴進料混合物依序在轉換區中及接著在隨後的二甲苯異構化區域中與兩種或更多種觸媒接觸以達成本發明之目標。此種兩觸媒系統透過有效的乙苯轉換及接著在低乙苯C8
芳族烴混合物中之有效二甲苯異構化而特別有效。可於任一區中使用呈固定床系統、移動床
系統、流化床系統、漿液系統、沸騰床系統或分批式操作之觸媒系統來實現接觸,但較佳在兩區中使用固定床系統。第一轉換區較佳包含於如上所述可有效轉換乙苯以及異構化二甲苯之條件下操作之本發明觸媒。該第一轉換區生成中間物流,及至少一部分及較佳全部中間物流未經進一步處理地在含有異構化觸媒之第二轉換區中接觸。異構化區域可包括單一反應器或兩個或更多個個別反應器且其間具有適宜構件以達成改良的接近二甲苯平衡。此兩種觸媒較佳裝納在同一反應器中。
該異構化區域較佳包含對二甲苯異構化特別有效之觸媒,乙苯已在第一區中轉換。可使用可有效用於此目的之任何觸媒,包括已知之選自MFI、MEL、EUO、FER、MFS、MTT、MTW、TON、MOR及FAU類型之沸石鋁矽酸鹽,其中pentasil沸石MFI及MTW為較佳。反應物可呈液相、液-氣混合相或氣相與第二觸媒接觸。操作條件一般係在以上針對本發明觸媒所述之範圍內,且在200℃至400℃範圍內之較低溫度對達成前文所述之較高範圍內之對-二甲苯比率為較佳。
用以自反應器之排出物回收異構化產物之特定方案不被視為係本發明之關鍵,及可使用相關技藝已知之任何有效回收方案。通常,轉換產物經分餾以移除輕質副產物(諸如烷烴、環烷烴、苯及甲苯)及重質副產物而獲得C8
異構體產物。重質副產物包括二甲基乙基苯及三甲苯。於一些實例中,可藉由選擇性分餾自異構化產物回收諸如鄰-二
甲苯或二甲基乙基苯之特定產物物種。源自C8
芳族烴轉換之產物通常經處理以視需要藉由結晶選擇性地回收對-二甲苯異構體。較佳係根據US 3,201,491使用結晶鋁矽酸鹽進行選擇性吸附。於以引用方式併入本文之US 3,626,020、US 3,696,107、US 4,039,599、US 4,184,943、US 4,381,419及US 4,402,832中說明於較佳吸附回收法中之改良及替代。
以下實例係僅提出用來說明本發明之一些具體實施例,而不應理解為限制陳述於申請專利範圍中之本發明範圍。如熟習此項相關技藝者所當明瞭,在本發明之精神內,存在許多可行的其他變動。
本發明第一觸媒之製備如下:於125 mL鐵氟龍(Teflon)內襯中,將11.8公克丙胺及4.0公克10% NaCl水溶液混合。將8.0公克具有Si/Al2
比為80之經煅燒油滴球形物添加至該混合物且經液相完全覆蓋。然後將該鐵氟龍內襯裝載於Parr反應器內繼而加熱至175℃維持10天。在冷卻至室溫之後,過濾出該等球形物並用去離子水洗滌。依據x射線繞射,該等經煅燒之觸媒顆粒包含70% MFI。藉由以含有0.08公克氯化四胺鉑及9.41公克NH4
NO3
之200毫升水溶液浸漬111公克煅燒產物,接著於100℃下蒸發,產生以觸媒顆粒成品計0.04質量%之最終鉑含量來製成觸媒。然後如US 7,939,701之實例1中所述,使浸漬樣本經歷二階段煅燒
及88℃銨離子交換,接著經歷480℃氧化及4-小時425℃還原。該觸媒具有0.718 cc/公克之ASTM D4284侵入體積及220 ppm之鉑含量且指示為觸媒A。
本發明第二觸媒之製備如下:於125 mL鐵氟龍內襯中,將15公克丁胺及10公克20% NaCl水溶液混合。將12公克具有Si/Al2為40之經煅燒油滴球形物添加至該混合物且經液相完全覆蓋。然後將該鐵氟龍內襯裝載於Parr反應器內繼而加熱至175℃維持10天。在冷卻至室溫之後,過濾出該等球形物並用DI水洗滌。依據x射線繞射,該等經煅燒之觸媒顆粒包含50% MFI。藉由以含有0.08公克氯化四胺鉑及9.41公克NH4
NO3
之200毫升水溶液浸漬111公克煅燒產物,接著於100℃下蒸發,產生以觸媒顆粒成品計0.04質量%之最終鉑含量來製成觸媒。然後如美國專利案第7,939,701號之實例1中所述使浸漬樣本經歷二階段煅燒及88℃銨離子交換,接著經歷480℃氧化及4-小時425℃還原。該觸媒具有0.743 cc/公克之ASTM D4284侵入體積及350 ppm之鉑含量且指示為觸媒B。
將本發明觸媒之性能與依據美國專利案第7,939,701號之實例2製得之已知技藝之參考觸媒作比較。藉由使實質上不存在對-二甲苯且含有15質量%乙苯、25質量%鄰-二甲苯及60質量%間-二甲苯之進料流異構化來進行各試驗。該等試驗係在4比1之氫對烴比率、7之重量每小時空間速度
及0.7 MPa表壓(gauge)之壓力下實施。於範圍自375℃至400℃之測試溫度下達成70%之乙苯轉換率。測量二甲苯之損耗及副產物甲苯及重質烷基苯之伴隨產量的性能如下:
本發明之兩觸媒當轉換乙苯時展現較參考觸媒低之二甲苯損耗及副產物產率,且提高產物中對-二甲苯之比例。應注意二甲苯損耗對乙苯轉換率之比率分別為0.016、0.006及0.027。
圖1顯示本發明顆粒之特徵。
Claims (9)
- 一種用於轉換非平衡C8 -芳族原料之方法,該方法包括使該原料與包含非結合沸石鋁矽酸鹽顆粒之觸媒床接觸,該等顆粒具有至少0.65 cc/公克之顆粒侵入孔隙體積及結晶度比例自低結晶度內部增加至高結晶度外部之顆粒結晶度梯度,該接觸係於轉換區中以包括340℃至500℃之溫度、100 kPa至5 MPa之壓力及2至50 hr-1 之質量每小時空間速度之轉換條件在氫存在下進行,以使乙苯轉換,其中二甲苯損耗低且獲得異構化產物,該產物含有較在該原料中更高比例之至少一種二甲苯異構體。
- 如請求項1之方法,其中該顆粒侵入孔隙體積為至少0.7 cc/公克。
- 如請求項1之方法,其中該觸媒顆粒之內部係界定為對應於經顆粒半徑之一半包圍之體積的顆粒部分。
- 如請求項1之方法,其中該觸媒顆粒之該內部係界定為該觸媒顆粒之內部50%之體積。
- 如請求項3或4之方法,其中該觸媒顆粒之該內部之該相對結晶度為10至50%。
- 如請求項3或4之方法,其中該觸媒顆粒之該外部之該相對結晶度為90至100%。
- 如請求項1或2之方法,其中該觸媒具有球形構形。
- 如請求項7之方法,其中該觸媒之該球形構形包括油滴之特徵。
- 如請求項1或2之方法,其中每%乙苯轉換,二甲苯損耗%係小於0.02%。
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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 |
US9643897B2 (en) | 2015-03-03 | 2017-05-09 | Uop Llc | Enhanced propylene production in OTO process with modified zeolites |
US10010878B2 (en) | 2015-03-03 | 2018-07-03 | Uop Llc | High meso-surface area, low Si/Al ratio pentasil zeolite |
MX2018005106A (es) | 2015-10-28 | 2018-06-06 | Bp Corp North America Inc | Catalizador mejorado para la conversion de etilbenceno en un proceso de isomerizacion de xileno. |
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