CN107537462A - Butane dehydrogenation butylene/butadiene catalyst and purposes - Google Patents
Butane dehydrogenation butylene/butadiene catalyst and purposes Download PDFInfo
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- CN107537462A CN107537462A CN201610498187.1A CN201610498187A CN107537462A CN 107537462 A CN107537462 A CN 107537462A CN 201610498187 A CN201610498187 A CN 201610498187A CN 107537462 A CN107537462 A CN 107537462A
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- catalyst
- butadiene
- butylene
- oxide
- butane dehydrogenation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 47
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title claims abstract description 30
- 239000001273 butane Substances 0.000 title claims abstract description 25
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000001802 infusion Methods 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- 230000019612 pigmentation Effects 0.000 claims abstract description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 230000001404 mediated effect Effects 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910016287 MxOy Inorganic materials 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- MAZOHJVAXBNBPX-UHFFFAOYSA-N ruthenium hydrochloride Chemical compound Cl.[Ru] MAZOHJVAXBNBPX-UHFFFAOYSA-N 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 18
- 235000013844 butane Nutrition 0.000 abstract description 16
- 239000007864 aqueous solution Substances 0.000 abstract description 15
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract description 8
- 229910000423 chromium oxide Inorganic materials 0.000 abstract description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000002905 metal composite material Substances 0.000 abstract 1
- 230000001172 regenerating effect Effects 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 15
- 238000007598 dipping method Methods 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 230000004913 activation Effects 0.000 description 8
- 238000001994 activation Methods 0.000 description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 241000219782 Sesbania Species 0.000 description 7
- 229920002472 Starch Polymers 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 235000019698 starch Nutrition 0.000 description 7
- 239000008107 starch Substances 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- NZIGZHDIUCTKQH-UHFFFAOYSA-N Cl[Ru+2].[NH4+] Chemical compound Cl[Ru+2].[NH4+] NZIGZHDIUCTKQH-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 2
- -1 carbon olefin hydrocarbon Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- RBNNPWUKDNRSMD-UHFFFAOYSA-N [Cl].[Ir] Chemical compound [Cl].[Ir] RBNNPWUKDNRSMD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical class [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical class [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Substances OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of butane dehydrogenation butylene/butadiene catalyst and application thereof, it is low mainly to solve to exist in existing technology of preparing butanes conversion, the problem of one way stability and regenerating stability difference.The oxide of at least one of IIIth A, IV A, V A, II B races element in zirconium oxide, chromium oxide and the periodic table of elements is introduced into alumina support by the present invention using dry pigmentation first, obtain metal composite oxide carrier, then using infusion process load iridium (Ir) and ruthenium (Ru) component, the aqueous solution of the soluble-salt of iridium (Ir) and ruthenium (Ru) is impregnated, catalyst is obtained after drying, calcination process.It is raw material by using normal butane, in 530~650 DEG C, 0.1~0.4MPa of reaction pressure of reaction temperature, 0.1~6.0h of normal butane mass space velocity‑1, H2O/CnH2n+2Volume ratio be 0.1~16 under the conditions of, raw material contacts with catalyst, reaction generate butylene/butadiene technical scheme preferably solve the problem, available for normal butane dehydrogenation butylene/butadiene catalyst it is industrially prepared in.
Description
Technical field
The present invention relates to a kind of carrier for butane dehydrogenation butylene/butadiene, catalyst and application thereof.
Background technology
Coproduction or by-product of the butylene/butadiene essentially from steam cracking and refinery factory fluid catalytic cracking process, can be wide
It is general to be used for synthetic polymer, rubber, resin, gasoline additive and various chemical intermediates.With low-carbon alkene demand increasingly
Increase, traditional production process is difficult to meet increasing rapidly for the market demand.The a large amount of low-carbon alkanes obtained by oil plant are liquid
The main component of liquefied oil gas, including a large amount of n-butane feedstocks, it is mainly used as domestic fuel.Exploitation is produced by low-carbon alkanes
Low carbon olefin hydrocarbon opens up new alkene, alkadienes source has important meaning for making full use of the comprehensive utilizations of low-carbon alkanes
Justice.Alkane catalytic dehydrogenation technology is using the Oleflex techniques of Uop Inc. and the Catofin techniques of Lummus companies as representative.And adopt
With normal butane be raw material it is state-of-the-art by the technique coproduction butylene of catalytic dehydrogenation and the technology of butadiene be Lummus companies
Houdry-Catadiene techniques, using Cr2O3/Al2O3Catalyst, conversion per pass about 50~60%, single pass life 5~10
Minute.It is domestic still without independent intellectual property right dehydrogenating low-carbon alkane producing light olefins production technology.
Low-carbon alkanes oxidative dehydrogenation process can be reacted at lower temperatures, and be carried out under oxygen atmosphere several
There is no carbon-collecting problem, catalyst need not frequently be regenerated, more advanced on process route, Chinese patent
(CN201210060733.5；CN201280067420.0；CN201210377874.x) disclose using sol-gel process, coagulate
The unknown primary catalyst of zirconium oxide-magnesia composite carrier load prepared by glue-Oxalic Acid Method and infusion process, the catalyst can
Butylene/butadiene, but butanes conversion only 30~50% are prepared for normal butane hydrocarbon dehydrogenation reaction, product selectivity 40~
50%, yield is less than 24%.Low-carbon alkanes direct dehydrogenation catalytic reaction generally use Cr systems or Pt systems dehydrogenation, it is necessary to
Carried out under high temperature, lower pressure, catalyst carbon deposit inactivation is serious, therefore develops urging for high activity, high selectivity and high stability
Agent turns into the key of the technology.Catalyst disclosed in Chinese patent (CN200710025372.X), in alumina modified
Porous molecular sieve be carrier on platinum-impregnated tin component preparation method, conversion of propane 17%, Propylene Selectivity 93%；It is Chinese special
Tin is introduced ZSM-5 molecular sieve carrier by sharp (CN200710023431.X) using the method using Hydrothermal Synthesiss, and uses infusion process
Supported Pt Nanoparticles component, after the catalyst is run 100 hours, conversion of propane is higher than 30%, Propylene Selectivity 99%.Chinese patent
(CN200710020064.8) and (CN200710133324.2) discloses a kind of platinum-tin catalyst and reacted for dehydrogenating propane, adopts
With tin component and the preparation method of platinum component co-impregnation, carrier is that molecular sieve containing Na, the catalyst such as Y types, ZSM-5 are continuously run
After 720 hours, conversion of propane 30.5%, Propylene Selectivity 96.4%, activity decrease after coke-burning regeneration.Chinese patent
(201280062907.X) employs a kind of aluminic acid zinc-manganese dehydrogenation that can need not contain noble metal, but one way stability compared with
Difference.U.S. Patent Publication uses zinc aluminate spinel to promote for auxiliary agents such as the Pt catalyst (US5430220) of carrier and Au, Ag
The aluminate carrier Pt catalyst (US3957688 entered；US4041099；US5073662), it is low all to there is conversion ratio in catalyst,
Selectively decline the problems such as obvious during use.Above-mentioned patent is to be directed to propane and dehydrogenation of isobutane catalyst, is related to just
Butane direct dehydrogenation catalyst patent report is less.
The content of the invention
One of technical problems to be solved by the invention are to provide a kind of new butane dehydrogenation catalyst, and the catalyst is used for
Normal butane dehydrogenation butylene/butadiene process, have under the conditions of high temperature and coke-burning regeneration, Catalyst Conversion is high, carbon deposit
Measure small, the advantages of single pass life is long.The two of the technical problems to be solved by the invention be to provide it is a kind of with solve technical problem it
The preparation method of one corresponding catalyst.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of butane dehydrogenation prepare butylene/
The catalyst carrier of butadiene, carrier composition include：a ZrO2·b Cr2O3·c MxOy·d Al2O3, wherein M is element week
At least one of IIIth A, IV A, V A, II B races, Al in phase table2O3Crystal phase structure is mixed with γ, θ；With percentage by weight
Meter, including following components：
a)ZrO2, the 10.0~25.0% of vehicle weight in terms of oxide；
b)Cr2O3, vehicle weight is calculated as with oxide 10.0~20.0%；
c)MxOy, vehicle weight is calculated as with oxide 5.0~15.0%；
d)Al2O3, vehicle weight is calculated as with oxide 50~70%.
In above-mentioned technical proposal, the carrier of catalyst is composite alumina support；Preferably ZrO2With Cr2O3Content is 15
~35%, Cr2O3/MxOy=1~3 (mass ratioes).The pore volume of preferable catalyst is in 0.2~0.9cm3/g；Preferably compare surface
Product scope is 20~200m2/ g, preferred specific surface area scope are 60~150m2/g；The oxide and M of aluminiumxOyOxide
The grain preferred size of diameter is at 10~120 microns.Carrier calcination temperature is 650~850 DEG C.
A kind of normal butane dehydrogenation prepares the catalyst of butylene/butadiene, by urging in active component and above-mentioned technical proposal
Agent carrier form, wherein active component be platinum metal be selected from Ir or Ru, with simple substance be calculated as catalyst weight 0.1~
1.0%.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows, and the preparation method of catalyst includes
Following steps：
A) by the desired amount of solid Al2O3、ZrO2、Cr2O3, in the IIIth A, IV A, V A, II B races in the periodic table of elements
At least one element oxide and pore creating material, ball milling 0.5~6 hour is carried out in ball mill, screening is more than 150 mesh
(standard screen) particle powder；Obtained particle powder is mediated, is calcined 1~36 hour at 550~800 DEG C after extrusion, produces institute
State catalyst carrier.
B) infusion process load active component on a catalyst support is used：The desired amount of chlorine iridium salt or ruthenium hydrochloride salt is water-soluble
Liquid, after impregnating 1~48 hour on a catalyst support, catalyst precarsor is obtained after drying；Catalyst precarsor is in fired, reduction
Obtain normal butane dehydrogenation and prepare butylene/butadiene catalyst.
Al in above-mentioned technical proposal2O3Crystal phase structure is mixed with γ, θ；The soild oxide, can be by nitrate
Decomposition obtains, and can also be obtained by metal oxidation reaction.Active component can be iridium or ruthenium one kind or two kinds, its precursor
It can be various water miscible salts or oxide, a small amount of alkali or alkali earth metal can also be added in active component and is used to subtract
Carbon deposit in few course of reaction, extend the single pass life of catalyst.
Different shapes can be made as needed for carrier, such as cylindric, spherical, sheet, tubular, Raschig ring or cellular
Deng, but it is cylindrical and it is spherical be relatively good selection, its effective diameter is in 1~7mm, in order to commercial Application.
A kind of method that normal butane dehydrogenation prepares butylene/butadiene, use normal butane as raw material, reaction temperature 520~
650 DEG C, 0~0.3MPa of reaction pressure；0.1~6.0h of alkane mass space velocity-1, H2O/CnH2n+2Volume ratio is 0.1~16 condition
Under, raw material and the generation butylene/butadiene of catalyst haptoreaction described in above-mentioned technical proposal.
In above-mentioned technical proposal, the preferred scope of reaction temperature is 550~610 DEG C；The preferred scope of reaction pressure is 0.1
~0.3MPa；The preferred scope of reaction velocity is 1.4~7.2h-1；H2O/CnH2n+2Volume ratio preferred scope is 2~15.
In above-mentioned technical proposal, it is preferred that the ratio of butylene and butadiene is (1：5)~(2：1)；It is furthermore preferred that butylene
Ratio with butadiene is (1：4)~(1：1).
Present invention employs dry pigmentation to prepare catalyst carrier, is added in the alumina support with a large amount of L acid sites
Cr2O3, SnO etc. there is the oxide of adsorption capacity to alkene, after containing these components in carrier, Product olefins can be increased
Absorption, increases the generation of secondary dehydrogenation product, so as to increase the content of butadiene in product.
Dehydrating alkanes reaction is continuously being carried out on the flowing miniature catalyst reaction device of quartz tube reactor.Product analysis uses
HP-5890 gas chromatographs (HP-AL/S capillary columns, 50m × 0.53mm × 15 μm；Fid detector) on-line analysis dehydrogenation production
Alkane, olefin(e) centent in thing simultaneously calculate conversion ratio, selectivity and the yield of reaction.The catalyst obtained using this method is existed
550 DEG C, normal pressure, butane mass space velocity 4.0 hours-1, H2O/C4H10For 6:Used under the conditions of 1, initial conversion is higher than 40%, fourth
Alkene/butadiene overall selectivity is stable, and higher than 85%, butadiene selective is higher than 50%, can be maintained through repeatedly regeneration, metallic
In below 3nm, catalyst performance stabilised, good technique effect is achieved.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
Take 26.0g zirconium oxides (ZrO2), 39.2g chromium oxide (Cr2O3), 7.0g antimony oxides (Sb2O3), 6.0g phosphorus pentoxides
(P2O5) and 121.7g aluminum oxide (Al2O3) mixture, add 9.0g starch, then carried out in ball mill mixing 200 points
Clock, screened with standard screen>200 mesh powder, about 6.5g sesbania powders, a small amount of 20% aqueous solution of nitric acid and appropriate are added in kneader
Water is mediated, extrusion, after 120 DEG C of drying, is calcined 10 hours at 680 DEG C, is obtained composite oxide catalysts carrier.Pore volume
0.52cm3/ g, specific surface area 86m2/g.The percentage by weight composition of gained catalyst carrier is shown in Table 1.
Obtained carrier loads upper active component using dipping technique, i.e., uses the carrier 15.0g dippings of gained at room temperature
Containing ammonium chloroiridate (NH4)2IrCl6, 0.12g) and 0.1g potassium nitrate 24 hours (metal iridium carrying capacity of the aqueous solution (10ml)
0.35%), then 60 DEG C of drying, 680 DEG C are calcined 3 hours in the air stream.Gained catalyst is designated as A.
Sample uses the reduction activation 90 minutes of 550 DEG C of hydrogen before dehydrogenation reaction, is reacted for butane dehydrogenation.
【Embodiment 2】
Take 47.0g zirconium oxides (ZrO2), 32.5g chromium oxide (Cr2O3), 10.5g bismuth oxides (Bi2O3), 3.6g five oxidation two
Phosphorus (P2O5) and 106.4g aluminum oxide (Al2O3) mixture, add 9.2g starch, mixing 180 then carried out in ball mill
Minute, screened with standard screen>200 mesh powder, about 6.5g sesbania powders, a small amount of 25% aqueous solution of nitric acid are added in kneader and is fitted
Amount water is mediated, extrusion, after 120 DEG C of drying, is calcined 10 hours at 680 DEG C, is obtained composite oxide catalysts carrier.Pore volume
0.57cm3/ g, specific surface area 93m2/g.The percentage by weight composition of gained catalyst carrier is shown in Table 1.
Obtained carrier loads upper active component using dipping technique, i.e., uses the carrier 15.0g dippings of gained at room temperature
Containing ammonium chloroiridate (NH4)2IrCl6(0.08g), ruthenium hydrochloride ammonium (NH4)2RuCl6(0.05g) and calcium nitrate the 0.22g aqueous solution
(10ml) 20 hours (metal dead weight capacity 0.33%), then 60 DEG C of drying, 680 DEG C are calcined 3 hours in the air stream.Gained is catalyzed
Agent is designated as B.
Sample uses hydrogen before dehydrogenation reaction, 520 DEG C of reduction activations 90 minutes, is reacted for butane dehydrogenation.
【Embodiment 3】
Take 25.2g zirconium oxides (ZrO2), 24.0g chromium oxide (Cr2O3), 10.6g bismuth oxides (Bi2O3), 5.2g cadmium oxides
(CdO), 4.2g stannous oxides (SnO) and 130.8g aluminum oxide (Al2O3) mixture, 8.8g starch is added, then in ball milling
Mixing 180 minutes is carried out in machine, is screened with standard screen>220 mesh powder, about 7.5g sesbania powders, a small amount of are added in kneader
20% aqueous solution of nitric acid and suitable quantity of water are mediated, extrusion, after 120 DEG C of drying, are calcined 10 hours at 680 DEG C, are obtained composite oxygen
Compound catalyst carrier.Pore volume 0.53cm3/ g, specific surface area 82m2/g.The percentage by weight composition of gained catalyst carrier is shown in Table
1。
Obtained carrier loads upper active component using dipping technique, i.e., uses the carrier 15.0g dippings of gained at room temperature
Containing ammonium chloroiridate (NH4)2IrCl620 hours (metal dead weight capacities of (0.11g) and potassium nitrate the 0.09g aqueous solution (10ml)
0.32%), then 60 DEG C of drying, 680 DEG C are calcined 3 hours in the air stream.Gained catalyst is designated as C.
Sample uses hydrogen before dehydrogenation reaction, 520 DEG C of reduction activations 90 minutes, is reacted for butane dehydrogenation.
【Embodiment 4】
Take 26.4g zirconium oxides (ZrO2), 24.4g chromium oxide (Cr2O3), 0.03g cupric oxide, 11.3g bismuth oxides (Bi2O3) and
137.9g aluminum oxide (Al2O3) mixture, add 9.0g starch, then carried out in ball mill mixing 180 minutes, with mark
Quasi- sieve screening>200 mesh powder, about 8.3g sesbania powders, a small amount of 30% aqueous solution of nitric acid and suitable quantity of water are added in kneader and is carried out
Mediate, extrusion, after 120 DEG C of drying, be calcined 10 hours at 680 DEG C, obtain composite oxide catalysts carrier.Pore volume 0.60cm3/
G, specific surface area 95m2/g.The percentage by weight composition of gained catalyst carrier is shown in Table 1.
Obtained carrier loads upper active component using dipping technique, i.e., uses the carrier 15.0g dippings of gained at room temperature
Containing ammonium chloroiridate (NH4)2IrCl6(0.03g), ruthenium hydrochloride ammonium (NH4)2RuCl6(0.08g) and potassium nitrate the 0.11g aqueous solution
(10ml) 20 hours (metal dead weight capacity 0.24%), then 60 DEG C of drying, 680 DEG C are calcined 3 hours in the air stream.Gained is catalyzed
Agent is designated as D.
Sample uses hydrogen before the reaction, 500 DEG C of reduction activations 90 minutes, is reacted for butane dehydrogenation.
【Embodiment 5】
Take 39.3g zirconium oxides (ZrO2), 25.3g chromium oxide (Cr2O3), 15.2g indium oxides (In2O3) and 120.2g aluminum oxide
(Al2O3) mixture, add 9.3g starch, then carried out in ball mill mixing 180 minutes, screened with standard screen>200
Mesh powder, about 8.2g sesbania powders, a small amount of 30% aqueous solution of nitric acid and suitable quantity of water are added in kneader and is mediated, extrusion, 120
DEG C drying after, 680 DEG C be calcined 10 hours, obtain composite oxide catalysts carrier.Pore volume 0.61cm3/ g, specific surface area
98m2/g.The percentage by weight composition of gained catalyst carrier is shown in Table 1.
Obtained carrier loads upper active component using dipping technique, i.e., uses the carrier 15.0g dippings of gained at room temperature
Containing ammonium chloroiridate (NH4)2IrCl620 hours (metal dead weight capacities of (0.08g) and calcium nitrate the 0.16g aqueous solution (10ml)
0.23%), then 60 DEG C of drying, 680 DEG C are calcined 3 hours in the air stream.Gained catalyst is designated as E.
Sample uses hydrogen before dehydrogenation reaction, 500 DEG C of reduction activations 90 minutes, is reacted for butane dehydrogenation.
【Embodiment 6】
Take 31.1g zirconium oxides (ZrO2), 30.7g chromium oxide (Cr2O3), 27.1g stannous oxides (SnO) and 111.1g oxidation
Aluminium (Al2O3) mixture, add 9.0g starch, then carried out in ball mill mixing 180 minutes, screened with standard screen>
200 mesh powder, about 8.2g sesbania powders, a small amount of 30% aqueous solution of nitric acid and suitable quantity of water are added in kneader and is mediated, extrusion,
After 120 DEG C of drying, it is calcined 10 hours at 680 DEG C, obtains composite oxide catalysts carrier.Pore volume 0.55cm3/ g, specific surface area
95m2/g.The percentage by weight composition of gained catalyst carrier is shown in Table 1.
Obtained carrier loads upper active component using dipping technique, i.e., uses the carrier 15.0g dippings of gained at room temperature
(the NH of ammonium containing ruthenium hydrochloride4)2RuCl620 hours (metal dead weight capacities of (0.10g) and calcium nitrate the 0.18g aqueous solution (10ml)
0.19%), then 60 DEG C of drying, 680 DEG C are calcined 3 hours in the air stream.Gained catalyst is designated as F.
Sample uses hydrogen before dehydrogenation reaction, 500 DEG C of reduction activations 90 minutes, is reacted for butane dehydrogenation.
【Embodiment 7】
Take 20.7g zirconium oxides (ZrO2), 39.2g chromium oxide (Cr2O3), 24.7g tin oxide (SnO2) and 115.3g aluminum oxide
(Al2O3) mixture, add 9.0g starch, then carried out in ball mill mixing 180 minutes, screened with standard screen>200
Mesh powder, about 8.3g sesbania powders, a small amount of 40% aqueous solution of nitric acid and suitable quantity of water are added in kneader and is mediated, extrusion, 120
DEG C drying after, 680 DEG C be calcined 10 hours, obtain composite oxide catalysts carrier.Pore volume 0.56cm3/ g, specific surface area
88m2/g.The percentage by weight composition of gained catalyst carrier is shown in Table 1.
Obtained carrier loads upper active component using dipping technique, i.e., uses the carrier 15.0g dippings of gained at room temperature
Containing ammonium chloroiridate (NH4)2IrCl620 hours (metal dead weight capacities of (0.1g) and calcium nitrate the 0.15g aqueous solution (10ml)
0.29%), then 60 DEG C of drying, 680 DEG C are calcined 3 hours in the air stream.Gained catalyst is designated as G.
Sample uses hydrogen before dehydrogenation reaction, 500 DEG C of reduction activations 90 minutes, is reacted for butane dehydrogenation.
【Comparative example 1】
Catalyst is prepared as described in Example 1, different carriers is added without composite assistant component only with aluminum oxide,
Activity component impregnation is carried out as carrier using alundum (Al2O3).
【Comparative example 2】
Catalyst is prepared as described in Example 1, and different carrier preparation process is added without chromium oxide component.
【Comparative example 3】
Catalyst is prepared as described in Example 1, and different carrier preparation process is added without zirconia components.
【Comparative example 4】
Catalyst is prepared as described in Example 1, and different carrier preparation process is added without the IIIth in the periodic table of elements
A, IV A, V A, II B races element oxide.
Table 1
【Embodiment 8~18】
Catalyst obtained by 1~comparative example of embodiment 4 is at 550 DEG C, normal pressure, normal butane mass space velocity 4.0 hours-1,
H2O/C4H10Volume ratio is 6:Evaluated under the conditions of 1, the results are shown in Table 2.
Table 2
【Embodiment 19】
Catalyst is prepared by each Step By Condition in embodiment 1 and examination catalyst, sample are used before dehydrogenation reaction
Hydrogen, 500 DEG C of reduction activations 90 minutes, for normal butane dehydrogenation reaction.Catalyst is at 550 DEG C, normal pressure, normal butane mass space velocity
4.0 hour-1, H2O/C4H10For 6:After being reacted 24 hours under the conditions of 1, being made charcoal 60 minutes at 500 DEG C using 1% air makes catalysis
Agent regenerates, and the initial performance after catalyst repeatedly regenerates is as shown in table 3.
Table 3
【Embodiment 20~26】
Embodiment 5 is subjected to performance evaluation under differential responses process conditions, the results are shown in Table 4.
Table 4
Claims (10)
1. a kind of butane dehydrogenation butylene/butadiene catalyst carrier, vehicle group turn into：a ZrO2·b Cr2O3·c MxOy·d
Al2O3, wherein M is at least one of the IIIth A, IV A, V A, II B races, Al in the periodic table of elements2O3Mixed with γ, θ phase
Synthetic phase structure；By weight percentage, including following components：
a)ZrO2, the 10.0~25.0% of vehicle weight in terms of oxide；
b)Cr2O3, vehicle weight is calculated as with oxide 10.0~20.0%；
c)MxOy, vehicle weight is calculated as with oxide 5.0~15.0%；
d)Al2O3, vehicle weight is calculated as with oxide 50~70%.
2. butane dehydrogenation butylene/butadiene catalyst carrier according to claim 1, it is characterised in that ZrO2With Cr2O3
Content is 15~35%.
3. butane dehydrogenation butylene/butadiene catalyst carrier according to claim 1, it is characterised in that Cr2O3/MxOy=
1~3 (mass ratio).
4. butane dehydrogenation butylene/butadiene catalyst carrier according to claim 1, it is characterised in that the hole of catalyst
Hold in 0.1~1.2cm3/g。
5. butane dehydrogenation butylene/butadiene catalyst carrier according to claim 1, it is characterised in that the ratio of catalyst
Surface area is in 1~300m2/g。
6. a kind of butane dehydrogenation butylene/butadiene catalyst, including described in active component and any one of Claims 1 to 5
Catalyst carrier, wherein active component include the Ir or Ru of platinum metal at least one, and catalyst weight is calculated as with simple substance
0.1~1.0%.
7. the preparation method of butane dehydrogenation butylene/butadiene catalyst described in claim 6, comprises the following steps：
A) dry pigmentation is used by the desired amount of solid Al2O3、ZrO2、Cr2O3, in the periodic table of elements the IIIth A, IV A, V A, II
The oxide and pore creating material of at least one of B races element, carry out ball milling 0.5~6 hour in ball mill, and screening is more than 150
Mesh (standard screen) particle powder；Obtained particle powder is mediated, after extruded moulding, is calcined 1~36 hour at 550~800 DEG C,
Produce the catalyst carrier.
B) infusion process load active component on a catalyst support is used：The desired amount of chloroiridate or ruthenium hydrochloride salt is water-soluble
Liquid, impregnate on a catalyst support, obtain catalyst precarsor after drying；Catalyst precarsor obtains normal butane in fired, reduction
Dehydrogenation butylene/butadiene catalyst.
8. the preparation method of butane dehydrogenation butylene/butadiene catalyst according to claim 7, it is characterised in that oxidation
Thing and MxOyOxide particle diameter is less than 180 microns.
9. a kind of method of butane dehydrogenation butylene/butadiene, uses normal butane as raw material, in 520~650 DEG C of reaction temperature,
0.1~0.3MPa of reaction pressure, 0.1~6.0h of alkane mass space velocity-1, H2O/CnH2n+2It is former under the conditions of volume ratio is 0.1~16
Material and the catalyst haptoreaction generation butylene and butadiene described in claim 1~8.
10. the method for butane dehydrogenation butylene/butadiene according to claim 9, it is characterised in that butylene and butadiene
Ratio be (1：5)~(2：1).
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