CN105712831A - Method used for preparing isobutene from mixture of methyl tertiary butyl ether and tert butyl alcohol - Google Patents
Method used for preparing isobutene from mixture of methyl tertiary butyl ether and tert butyl alcohol Download PDFInfo
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- CN105712831A CN105712831A CN201410717047.XA CN201410717047A CN105712831A CN 105712831 A CN105712831 A CN 105712831A CN 201410717047 A CN201410717047 A CN 201410717047A CN 105712831 A CN105712831 A CN 105712831A
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- alumina
- mtbe
- tba
- amorphous silica
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 title claims abstract description 169
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 120
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 86
- 239000000203 mixture Substances 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 112
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 40
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 31
- 239000010703 silicon Substances 0.000 claims abstract description 31
- -1 stannum modified aluminium oxide Chemical class 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 103
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 50
- 230000004048 modification Effects 0.000 claims description 22
- 238000012986 modification Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000003213 activating effect Effects 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- FVNIMHIOIXPIQT-UHFFFAOYSA-N 2-methoxybutane Chemical compound CCC(C)OC FVNIMHIOIXPIQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 20
- 230000018044 dehydration Effects 0.000 abstract description 16
- 238000006297 dehydration reaction Methods 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000011258 core-shell material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 25
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 21
- 239000002002 slurry Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 15
- 239000011230 binding agent Substances 0.000 description 14
- 229910021417 amorphous silicon Inorganic materials 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- 239000004411 aluminium Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 229910001593 boehmite Inorganic materials 0.000 description 11
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 11
- 239000008188 pellet Substances 0.000 description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 239000005046 Chlorosilane Substances 0.000 description 7
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 7
- 238000007493 shaping process Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 235000014121 butter Nutrition 0.000 description 6
- 210000002966 serum Anatomy 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 5
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VUQVJIUBUPPCDB-UHFFFAOYSA-N (1-bromo-2,2-diphenylethenyl)benzene Chemical compound C=1C=CC=CC=1C(Br)=C(C=1C=CC=CC=1)C1=CC=CC=C1 VUQVJIUBUPPCDB-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 241001292396 Cirrhitidae Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- GTPDFCLBTFKHNH-UHFFFAOYSA-N chloro(phenyl)silicon Chemical compound Cl[Si]C1=CC=CC=C1 GTPDFCLBTFKHNH-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000013433 optimization analysis Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a method used for preparing isobutene from a mixture of methyl tertiary butyl ether (MTBE) and tert butyl alcohol (TBA). According to the method, the mixture of MTBE and TBA is contacted with a catalyst A and a catalyst B successively so as to prepare isobutene via reaction, wherein the catalyst A and the catalyst B are novel catalysts with different core-shell ratio, amorphous silica-alumina is taken as the core, and the shell is silicon and stannum modified aluminium oxide. According to the method, isobutene production is realized via simultaneous MTBE cracking and TBA dehydration, conversion rate of TBA and conversion rate of MTBE are both relatively high, and selectivity of isobutene production is relatively high.
Description
Technical field
The present invention relates to a kind of MTBE(methyl tertiary butyl ether(MTBE)) and the TBA(tert-butyl alcohol) compound while cracking for the method for isobutene..
Background technology
Isobutene. is important Organic Chemicals, with it for raw material mainly for the production of fine chemical products such as methyl methacrylate (MMA), butyl rubber, polyisobutylene, tertiary butyl phenol, tert-butylamine, methylallyl chloride, trimethylace tonitric, isoprene, p-tert-octyl phenol, antioxidant, agriculture medicine intermediate, tert-butyl acetate, silane.The raw material producing isobutene. is mainly derived from the by-product C-4-fraction of naphtha steam cracking ethylene unit, the by-product tert-butyl alcohol etc. in the by-product C-4-fraction of refinery fluid catalytic cracking (FCC) device and the synthesis of Halcon method expoxy propane, wherein industrial process mainly has the cracking of sulphuric acid extraction, adsorption method of separation, tert-butyl alcohol dehydration method, methyl tertiary butyl ether(MTBE) and n-butene isomerization process etc..
MTBE cracking is many a kind of methods preparing advanced technology in isobutene. method, better economy.In MTBE cracking isobutene reaction process, primary response is under the effect of catalyst, and MTBE is cracked into isobutene. and methanol, obtains isobutene. or high-purity isobutene. after through operations such as rectification.The catalyst type of MTBE cracking isobutene. is more, including aluminium oxide, silicon oxide, amorphous silica-alumina, ion exchange resin, molecular sieve, solid phosphoric acid and other acidic resin catalyst systems.MTBE cracking isobutene catalyst as disclosed in CN1853772A, CN102451674A, JP2004115407, JP2004091443, JP3220136 etc. is amorphous silicon aluminum-based catalyst, for another example patent DE3509292, DE3210435, US4447668, GB1482883, US4570026, US4551567 etc. then adopt ion-exchange resin catalyst catalyst, again for another example patent CN96123535.7, EP0118085, JP7626401, JP7494602 etc. using solid phosphoric acid, sulfate, activated carbon as MTBE catalyst for cracking.
Another the comparatively general method producing isobutene. is TBA dehydration.The reaction of TBA Dehydration isobutene. has the features such as by-product is few, separation and purification easy, reduced investment.Conventional catalyst includes aluminium oxide, molecular sieve, sulfonic acid ion exchange resin etc..Isobutene. dehydration catalyst as disclosed in US3665048, CN101300211A, CN102516030A etc. is alumina series catalyst.For another example US4423271, US2005/0014985A1 etc. are with sulfonate resin for catalyst.The catalyst for tert-butyl alcohol cracking reaction that CN103611572A and CN103506158A provides, it is prepared by following methods: first pass through melt pelletization method by pelletize after blended to polystyrene, chliorinated polyvinyl chloride, polytrifluorochloroethylene and Kynoar or poly-phenylstilbene bromide, melted, then granulated carry out sulfonating reaction with sulfur trioxide and obtain described catalyst.
In production process, more often meet MTBE and TBA compound.Its main source has two kinds.The first source is the TBA that the driving initial stage being waste MTBE with isobutene. and methanol can produce more amount.This is because when going into operation, catalyst or (and) install pipes in may adulterate a certain amount of water, excessive isobutene. reacts with water and is readily generated TBA.For commercial plant, also imply that having considerable amount of MTBE and TBA product mix at the initial stage of going into operation generates.MTBE and TBA product mix is as waste disposal, or adopts MTBE/TBA knockout tower to be easily separated, and respectively obtains target product MTBE and TBA.
The second source is also most important source is artificial production, i.e. coproduction TBA while preparing MTBE.First, it is that the technology producing TBA specially exists some problems.TBA production technology is complex, and owing to the intersolubility of C-4-fraction Yu water is poor, therefore TBA product design only has 45%-55%, and TBA is difficult to separate with water azeotropic in addition, and conventional distillation can only obtain the TBA of 85%.It is typically employed to multitple extraction rectification and just can obtain the TBA product of higher concentration, but equipment investment and operating cost will increase substantially.Secondly, while preparing MTBE, coproduction TBA has technical advantage: (1) scheme simple and flexible.According to product demand commercially, process program suitably can be adjusted.Only technological process simply need to be switched and change suitable catalyst, so that it may realize per unit area yield MTBE or TBA and MTBE and TBA mixture.(2) flow process is convenient to carry out, and investment risk is little.Just can be easy to transfer joint production process to by per unit area yield MTBE technique carries out transformation, it is simple to implement.Can returning to again traditional per unit area yield technique easily, MTBE/TBA knockout tower more than needed can be used to carry out the separation of n-butene in C-4-fraction simultaneously.Therefore, this technology is absent from investment risk.Finally, combined production device investment cost is low.If there are special per unit area yield MTBE and special per unit area yield TBA device, the two each architectonical in manufacturer, equipment can not be used each other, therefore many than the equipment of joint production process, and investment is big.Combined production device can produce MTBE and TBA simultaneously, produces MTBE and TBA than newly-built two sets respectively with scale set and reduces investment outlay more than 40%, also decreases operating cost significantly simultaneously.Therefore, while preparing MTBE, coproduction TBA technology obtains extensive attention.The Lu Chunlong of Xi'an Petroleum University, in its Master's thesis " the optimization analysis of MTBE device and the coproduction with TBA relate to pre-test ", has carried out serious analysis with regard to coproduction TBA technology while preparing MTBE, has obtained answer certainly.CN200610104876.6 discloses the isobutene. in a kind of C-4-fraction and the production method of methanol-water coproducing methyl tertbutyl ether and the tert-butyl alcohol.But MTBE and the TBA compound product of coproduction, main whereabouts is to adopt MTBE/TBA knockout tower to be easily separated, and respectively obtains target product MTBE and TBA.
Whether MTBE and the TBA compound that the first source or the second source obtain, present stage, compound is used as when producing isobutene., substantially all adopt and obtain purer MTBE raw material and TBA raw material after being separated by compound, then on MTBE cracker and TBA dehydration device, distinguish preparing isobutene respectively.
Carrying out cracking isobutene. technology about MTBE and TBA compound, present stage is still blank.One of them important reason be MTBE cracker and TBA dehydration device the requirement of catalyst performance is inconsistent.It is generally believed that the active sites on MTBE catalyst for cracking surface is based on Bronsted acid (B-acid) center, and the catalyst of TBA Dehydration isobutene. is Lewis acid (L acid) catalytic reaction process.For single kind catalyst, or based on B-acid, or based on L acid, it is impossible to both take into account.Another reason, adopts common catalyst, and both reaction conditions are different, and especially reaction temperature, TBA dehydration temperaturre is lower compared with MTBE cracking temperature.Therefore, how under same device same reaction conditions, to process MTBE and TBA compound to produce isobutene. simultaneously, there is higher activity and selectivity simultaneously, be an important subject of this area.
Summary of the invention
In order to realize preparing isobutene. with MTBE and TBA compound for raw material, a kind of method that the invention provides MTBE and TBA compound preparing isobutene.The method not only can realize MTBE and TBA simultaneous reactions and generate isobutene., and MTBE and TBA is respectively provided with higher conversion ratio, and side reaction is few, and isobutene. reaches higher selectivity.
The present invention prepares the method for isobutene., adopt fixed-bed process, at least adopt the beds of two series connection, contact to react with catalyst A and catalyst B successively including MTBE and TBA compound and prepare isobutene., catalyst A wherein used contains nucleocapsid structure component, core is amorphous silica-alumina, shell is the aluminium oxide by silicon and tin modification, it is wherein 1:18～1:3 by the weight ratio of the aluminium oxide of silicon and tin modification Yu amorphous silica-alumina, preferred 1:10～1:4, by in the aluminium oxide of silicon and tin modification, silicone content is 0.5wt%～2.0wt%, Theil indices is 0.2wt%～1.0wt%, being preferably silicone content is 0.8wt%～1.5wt%, Theil indices is 0.3wt%～0.8wt%；Catalyst B contains nucleocapsid structure component, core is amorphous silica-alumina, shell is the aluminium oxide by silicon and tin modification, it is wherein 1:60～1:20 by the weight ratio of the aluminium oxide of silicon and tin modification Yu amorphous silica-alumina, it is preferable that 1:50～1:30, by the aluminium oxide of silicon and tin modification, silicone content is 0.5wt%～2.0wt%, Theil indices is 0.2wt%～1.0wt%, it is preferred to silicone content is 0.8wt%～1.5wt%, and Theil indices is 0.3wt%～0.8wt%.
Two beds can be seated in different reactors by the inventive method respectively, it is also possible to is seated in a reactor.
In the inventive method, the admission space of catalyst A and catalyst B is than for 1:1～1:10, it is preferred to 1:2～1:5.
In catalyst A of the present invention or catalyst B, in described amorphous silica-alumina, SiO2Content is 60.0wt%～99.0wt%, preferably 80.0wt%～95.0wt%, it is preferred to 87.0wt%～93.0wt%；Al2O3Content is 1.0wt%～40.0wt%, preferably 5.0wt%～20.0wt%, it is preferred to 7.0wt%～13.0wt%.
In catalyst A of the present invention or catalyst B, the character of described amorphous silica-alumina is as follows: specific surface area is 240m2/ g～450m2/ g, it is preferable that 270m2/ g～410m2/ g；Pore volume is 0.4mL/g～0.9mL/g, it is preferable that 0.5mL/g～0.7mL/g.
The method of MTBE and TBA compound preparing isobutene of the present invention adopts fixed-bed process.The reaction condition adopted is: during total liquid, volume space velocity is 0.5h-1～10.0h-1, it is preferred to 2.0h-1～5.0h-1；Temperature is 120 DEG C～300 DEG C, it is preferred to 150 DEG C～250 DEG C；Pressure is normal pressure～0.6MPa, it is preferred to normal pressure～0.3MPa.
In the inventive method, in MTBE and TBA compound, the weight ratio of MTBE and TBA is the compound of 1:1 ~ 40:1, it is preferable that the weight ratio of MTBE and TBA is 2:1 ~ 20:1.
Catalyst A of the present invention or catalyst B can adopt following method to prepare, including: chlorosilane and sn-containing compound are added separately in the aluminum hydroxide slurry of constantly stirring and obtain siliceous and stannum aluminum hydroxide slurry, above-mentioned siliceous and stannum aluminum hydroxide slurry is sprayed on amorphous silica-alumina, then drying and roasting, obtains catalyst of the present invention.Those skilled in the art adjust catalyst composition according to said method, can obtain catalyst A or catalyst B.
In the inventive method, chlorosilane and sn-containing compound are added in the aluminum hydroxide slurry of constantly stirring preferably with the mode being slowly added to or instilling.
Amorphous silica-alumina of the present invention can adopt method conventional in prior art to prepare amorphous silica-alumina, such as coprecipitation, step-by-step precipitation method and mechanical mixing, the amorphous silica-alumina preferably obtained after saturated vapor processes, wherein treatment temperature is 150 DEG C～450 DEG C, and the process time is 5h～24h.
Amorphous silica-alumina of the present invention preferably employs the amorphous silica-alumina containing activating agent.Described activating agent is selected from one or more in group iia and group VIII metal, and wherein group iia metal is preferably one or more in Be, Mg and Ca, and group VIII metal is preferably one or more in Ni, Pd and Pt.With the weight of the amorphous silica-alumina containing activating agent for benchmark, the content of activating agent oxide is 0.3wt%～2.0wt%.In the present invention, active agent component can saturated steam process before load, can also at the back loading of saturated steam process, carrying method can adopt infusion process, detailed process is as follows: immersed by amorphous silica-alumina in the aqueous solution of the soluble inorganic salt containing activating agent, activator solution concentration is 0.08mol/L～2.0mol/L, then through 200 DEG C～600 DEG C roastings 3～8 hours after dipping.
In the inventive method, aluminum hydroxide slurry is generally adopted boehmite serosity.Boehmite has another name called monohydrate alumina or false boehmite, and molecular formula is AlOOH nH2O(n=0.08～0.62).Aluminum hydroxide slurry adopts conventional method to prepare, including acid system or alkaline process, the NaA1O of aluminium alcoholates Hydrolyze method, aluminium salt or aluminate2Solution passes into CO2Carbonizatin method etc..
In the inventive method, the chlorosilane of the preferred facile hydrolysis of chlorosilane, can be one or more in dimethyldichlorosilane, trim,ethylchlorosilane, phenyl chlorosilane etc..Wherein, 0.5wt%～2.0wt% that the addition (counting with silicon) of chlorosilane is aluminium hydroxide (in aluminium oxide) weight, it is preferable that 0.8wt%～1.5wt%.
In the inventive method, the sn-containing compound of the preferred facile hydrolysis of sn-containing compound, one or more in including stannum dichloride, butter of tin, nitric acid stannum, stannous sulfate, stannous octoate, dibutyl tin dichloride etc..Wherein, 0.2wt%～1.0wt% that the addition (counting with stannum) of sn-containing compound is aluminium hydroxide (in aluminium oxide) weight, it is preferable that 0.3wt%～0.8wt%.
Catalyst used by the present invention is preformed catalyst, shaping of catalyst can carry out (such as first by amorphous silica-alumina molding before siliceous and stannum aluminum hydroxide slurry sprays amorphous silica-alumina, after drying and roasting, spray siliceous and stannum aluminum hydroxide slurry, final catalyst is obtained) then through after dry and roasting, can also carry out (such as after siliceous and stannum aluminum hydroxide slurry sprays amorphous silica-alumina, siliceous and stannum aluminum hydroxide slurry is sprayed without on the amorphous silica-alumina of molding, then after drying or dry and roasting, then through molding, dry and roasting, obtain final catalyst).In the inventive method, dry and roasting involved in catalyst preparation process is generally adopted normal condition and carries out, such as drying condition: dry 1h ~ 24h, roasting condition: at 400 DEG C～700 DEG C, it is preferable that roasting 1h ~ 24h at 450 DEG C～600 DEG C at 80 DEG C ~ 150 DEG C.
In the inventive method, molding can adopt the forming method of routine, such as prepares spherical, can adopt oil drop method, rotary type comminution granulation, the marumerizer method of forming etc., and its geometric diameter is between 1.0mm-5.0mm, it is desirable to elect 2.0mm-3.0mm as.In the inventive method, in forming process, it is also possible to add binding agent and shaping assistant, binding agent can adopt the binding agent of routine, is generally little porous aluminum oxide, accounts for the 5.0wt%～20.0wt% of final catalyst weight.Shaping assistant is sesbania powder or methylcellulose such as, accounts for the 1.5wt%～3.0wt% of final catalyst weight.
The inventive method has been particularly suitable for preparing isobutene reaction with MTBE and TBA compound for raw material, namely MTBE cracking isobutene. and TBA Dehydration isobutene reaction can carry out simultaneously, by adopting two kinds of catalyst to carry out grating, it is not only able to improve MTBE and TBA and changes into isobutene., and the selectivity of isobutene. can be improved.
The inventive method can adopt conventional reactor, such as adopts original MTBE cracking isobutene. device or TBA Dehydration isobutene. device.
In the inventive method, the impurity contained in raw material when impurity in compound is that isobutene. prepared by raw material and TBA is raw material dehydration preparing isobutene equal to or less than conventional MTBE, such as methyl sec-butyl ether≤0.2wt%, methanol≤0.05wt%, isobutylene oligomer≤0.05wt%, carbon four and carbon less than four hydro carbons≤0.1wt%.
The present invention is in preparing catalyst process, the chlorosilane and the sn-containing compound that add in aluminum hydroxide slurry are hydrolyzed respectively, the active center of the TBA dehydration being suitable for can be provided for shell aluminium oxide, simultaneously silicon and other groups (including organic group, acidic-group etc.) have the connectivity benefiting pore distribution and shell and the stratum nucleare duct improving catalyst shell, be conducive to compound to react and be diffused rapidly to stratum nucleare.It addition, the acid (including hydrochloric acid etc.) generated when chlorosilane and sn-containing compound hydrolysis also can increase slurry viscosity, making catalyst structure more uniform, nucleocapsid combines tightr.This catalyst is that processing MTBE and TBA compound is prepared isobutene. and provided excellent performance simultaneously, is that existing catalyst is beyond one's reach.
The present invention is by synthesizing a kind of raw catelyst, for with MTBE and TBA compound for the reaction of raw material generation isobutene., make TBA dehydration and MTBE crack two kinds of reactions and be prepared isobutene. simultaneously, avoid the separation process of MTBE and TBA compound, and avoid construction MTBE cracker and TBA dehydration device respectively to produce isobutene., save operating procedure, reduce cost of investment, and making the conversion ratio of the conversion ratio of TBA and MTBE all higher, the selectivity generating isobutene. is also higher.
Detailed description of the invention
In the present invention, material purity and product composition adopt gas chromatography analysis.Specific surface area and pore volume are to adopt low temperature liquid nitrogen determination of adsorption method.Constituent content adopts inorganic analysis method to measure.In the present invention, wt% is mass fraction.
Comparative example 1
By amorphous silicon aluminium powder FM1(wherein SiO2Content 92.1wt%, specific surface area is 281m2/ g, pore volume is 0.58mL/g) it is immersed in appropriate Ni (NO3)212h in aqueous solution, by 400 DEG C of roasting 6h, then through 300 DEG C, 6h saturated vapor process after, must containing the amorphous silicon aluminium powder FM1-1 that nickel oxide is 0.61wt%.
It is 21.3wt% by aluminum hydroxide slurry LRJ1(solid content) spray on FM1-1, dry 4h at 120 DEG C, roasting 6h at 500 DEG C, it is subsequently adding little porous aluminum oxide that weight accounting is 10wt% as binding agent, it is shaped to grain size catalyst pellet between 2.2mm-2.5mm with the marumerizer method of forming, at 120 DEG C, dry 15h, obtains catalyst DB-1 through 450 DEG C of roasting 6h, and wherein aluminium hydroxide counts the weight ratio with amorphous silica-alumina for 1:10 with aluminium oxide.Concrete evaluation result is in Table 1, table 4.
Comparative example 2
Under agitation, in the aluminum hydroxide slurry LRJ1 in comparative example 1, nitric acid stannum, stannous octoate, dimethyldichlorosilane it are slowly added respectively.Obtaining siliceous and stannum mixed serum (LRJ1-2), wherein nitric acid stannum and stannous octoate account for the boehmite (aluminium hydroxide) 0.38wt% in alumina weight in the addition of stannum, and the mol ratio of nitric acid stannum and stannous octoate is 1:1；Dimethyldichlorosilane accounts for the boehmite 1.23wt% in alumina weight in the addition of silicon.Then dry 4h at 120 DEG C, at 500 DEG C, roasting 6h obtains siliceous and stannum alumina powder LRJ1-3.
By FM1-1 and the LRJ1-3 in comparative example 1 with weight ratio 10:1 Homogeneous phase mixing, it is subsequently adding little porous aluminum oxide that weight accounting is 10wt% as binding agent, it is shaped to grain size catalyst pellet between 2.2mm-2.5mm with the marumerizer method of forming, at 120 DEG C, dry 4h, obtains catalyst DB-2 through 400 DEG C of roasting 16h.Concrete evaluation result is in Table 1, table 4.
Comparative example 3
By the dry 4h at 120 DEG C of the aluminum hydroxide slurry LRJ1 in comparative example 1, roasting 6h at 500 DEG C, it is subsequently adding little porous aluminum oxide that weight accounting is 10wt% as binding agent, it is shaped to grain size catalyst pellet between 2.2mm-2.5mm with the marumerizer method of forming, at 120 DEG C, dry 4h, obtains catalyst DB-3 through 400 DEG C of roasting 16h.Concrete evaluation result is in Table 2.
Comparative example 4
Siliceous and the stannum alumina powder LRJ1-3 that comparative example 2 is obtained, adding weight accounting is that the little porous aluminum oxide of 10wt% is as binding agent, it is shaped to grain size catalyst pellet between 2.2mm-2.5mm with the marumerizer method of forming, at 120 DEG C, dry 4h, obtains catalyst DB-4 through 400 DEG C of roasting 6h.Concrete evaluation result is in Table 2.
Comparative example 5
Amorphous silicon aluminium powder FM1-1 in comparative example 1 is added little porous aluminum oxide that weight accounting is 10wt% as binding agent, it is shaped to grain size catalyst pellet between 2.2mm-2.5mm with the marumerizer method of forming, dry 4h at 120 DEG C, obtaining catalyst DB-5 through 450 DEG C of roasting 12h, its MTBE cracks evaluation result in Table 3.
Embodiment 1
The aluminum hydroxide slurry LRJ1-2 of the stanniferous and silicon in comparative example 2 is sprayed on the amorphous silicon aluminium powder FM1-1 in comparative example 1, then dry 4h, roasting 6h at 500 DEG C at 120 DEG C.It is subsequently adding little porous aluminum oxide that weight accounting is 10wt% as binding agent, it is shaped to grain size catalyst pellet between 2.2mm-2.5mm with the marumerizer method of forming, dry 4h at 120 DEG C, obtain catalyst SL-1 through 400 DEG C of roasting 6h, be wherein 1:10 by the weight ratio of the aluminium oxide of silicon and tin modification Yu amorphous silica-alumina.Concrete evaluation result is in Table 1.
Embodiment 2
Under agitation, to aluminum hydroxide slurry LRJ2(solid content 31.2wt%) in be slowly added butter of tin, trim,ethylchlorosilane respectively.Obtaining siliceous and stannum mixed serum (LRJ2-2), wherein butter of tin accounts for the boehmite 0.65wt% in alumina weight in the addition of stannum；Trim,ethylchlorosilane accounts for the boehmite 0.85wt% in alumina weight in the addition of silicon.This serosity is sprayed on the amorphous silicon aluminium powder FM1-1 in comparative example 1, then dry 8h, roasting 3h at 600 DEG C at 90 DEG C.It is subsequently adding the methylcellulose of little porous aluminum oxide that weight accounting is 7.5wt% and 2.0wt% respectively as binding agent and shaping assistant, it is shaped to grain size catalyst pellet between 2.6mm-2.9mm with the marumerizer method of forming, dry 8h at 90 DEG C, obtain catalyst SL-2 through 650 DEG C of roasting 3h, be wherein 1:20 by the weight ratio of the aluminium oxide of silicon and tin modification Yu amorphous silica-alumina.Concrete evaluation result is in Table 1.
Embodiment 3
By amorphous silicon aluminium powder FM2(wherein SiO2Content 82.2wt%, Al2O3Content is 17.8wt%；Specific surface area is 335m2/ g, pore volume is 0.78mL/g) through 200 DEG C, after 16h saturated vapor processes, be immersed in appropriate Be (NO3)2In aqueous solution (solution concentration is 1.50mol/L), must containing the amorphous silicon aluminium powder FM2-1 that beryllium oxide is 1.02wt% by 500 DEG C of roasting 5h.The mixed serum LRJ1-2 of the stanniferous and silicon in comparative example 2 is sprayed on amorphous silicon aluminium powder FM2-1, then dry 1.5h, roasting 4h at 650 DEG C at 150 DEG C.It is subsequently adding little porous aluminum oxide that weight accounting is 18wt% as binding agent, it is shaped to grain size catalyst pellet between 2.2mm-2.5mm with the marumerizer method of forming, dry 4h at 120 DEG C, obtain catalyst SL-3 through 400 DEG C of roasting 6h, be wherein 1:25 by the weight ratio of the aluminium oxide of silicon and tin modification Yu amorphous silica-alumina.Concrete evaluation result is in Table 1.
Embodiment 4
The mixed serum LRJ2-2 of the stanniferous and silicon in embodiment 2 is sprayed on the amorphous silicon aluminium powder FM2-1 in embodiment 3, then dry 10h, roasting 6h at 500 DEG C at 80 DEG C.It is subsequently adding the sesbania powder of little porous aluminum oxide that weight accounting is 5wt% and 3.0wt% respectively as binding agent and shaping assistant, it is shaped to grain size catalyst pellet between 2.4mm-2.7mm with the marumerizer method of forming, dry 4h at 120 DEG C, obtain catalyst SL-4 through 700 DEG C of roasting 6h, be wherein 1:5 by the weight ratio of the aluminium oxide of silicon and tin modification Yu amorphous silica-alumina.Concrete evaluation result is in Table 1.
Embodiment 5
Under agitation, in the aluminum hydroxide slurry LRJ2 in embodiment 2, butter of tin, trim,ethylchlorosilane it are slowly added respectively.Obtaining siliceous and stannum mixed serum (LRJ2-2), wherein butter of tin accounts for the boehmite 0.65wt% in alumina weight in the addition of stannum；Trim,ethylchlorosilane accounts for the boehmite 0.85wt% in alumina weight in the addition of silicon.This serosity is sprayed on the amorphous silicon aluminium powder FM1-1 in comparative example 1, then dry 8h, roasting 3h at 600 DEG C at 90 DEG C.It is subsequently adding binding agent and shaping assistant, it is shaped to grain size catalyst pellet between 2.6mm-2.9mm with the marumerizer method of forming, at 90 DEG C, dry 8h, obtains catalyst SL-5 through 550 DEG C of roasting 3h, is wherein 1:8 by the weight ratio of the aluminium oxide of silicon and tin modification Yu amorphous silica-alumina.Concrete evaluation result is in Table 1, table 2, table 4.
Embodiment 6
Under agitation, in the aluminum hydroxide slurry LRJ2 in embodiment 2, stannous octoate, dimethyldichlorosilane it are slowly added respectively.Obtaining siliceous and stannum mixed serum (LRJ2-2), wherein butter of tin accounts for the boehmite 0.65wt% in alumina weight in the addition of stannum；Trim,ethylchlorosilane accounts for the boehmite 0.85wt% in alumina weight in the addition of silicon.This serosity is sprayed on the amorphous silicon aluminium powder FM1-1 in comparative example 1, then dry 8h, roasting 3h at 600 DEG C at 90 DEG C.It is subsequently adding binding agent and shaping assistant, it is shaped to grain size catalyst pellet between 2.6mm-2.9mm with the marumerizer method of forming, at 90 DEG C, dry 8h, obtains catalyst SL-6 through 550 DEG C of roasting 3h, is wherein 1:40 by the weight ratio of the aluminium oxide of silicon and tin modification Yu amorphous silica-alumina.Concrete evaluation result is in Table 1, table 2, table 4.
The fixed-bed process evaluation result of table 1 comparative example 1-2 and embodiment 1-6 prepared catalyst
| Grating 1 | Grating 2 | Grating 3 | Grating 4 | Grating 5 | Grating 6 | Grating 7 | Grating 8 | |
| Catalyst A | SL-1 | DB-2 | SL-1 | SL-1 | SL-5 | SL-5 | SL-4 | SL-4 |
| Catalyst B | DB-1 | SL-2 | SL-2 | SL-6 | SL-3 | SL-2 | SL-6 | SL-3 |
| Catalyst A and catalyst B volume ratio | 1:3 | 1:3 | 1:3 | 1:3 | 1:2 | 1:4 | 1:1 | 1:10 |
| Volume space velocity during total liquid, h-1 | 2.5 | 2.5 | 2.5 | 3.0 | 5.0 | 3.0 | 3.0 | 2.0 |
| Volume space velocity during MTBE liquid, h-1 | 1.8 | 1.8 | 1.8 | 2.0 | 3.0 | 2.0 | 2.0 | 1.5 |
| Volume space velocity during TBA liquid, h-1 | 0.7 | 0.7 | 0.7 | 1.0 | 2.0 | 1.0 | 1.0 | 0.5 |
| Reaction temperature, DEG C | 210 | 210 | 210 | 210 | 250 | 210 | 210 | 155 |
| Reaction pressure, MPa | 0.05 | 0.05 | 0.05 | 0.05 | 0.30 | 0.05 | 0.05 | Normal pressure |
| MTBE conversion ratio, wt% | 96.5 | 98.3 | 99.2 | 99.3 | 99.6 | 99.7 | 99.8 | 97.6 |
| TBA conversion ratio, wt% | 91.3 | 92.1 | 99.6 | 99.5 | 99.5 | 99.5 | 99.8 | 99.2 |
| Selective isobutene, wt% | 98.7 | 99.0 | 99.8 | 99.8 | 99.9 | 99.8 | 99.9 | 99.6 |
As can be seen from Table 1, the nucleus shell catalyst adopting two kinds of different compositions carries out grating, organically coordinated by both, MTBE cracking can be realized when fixed-bed process and TBA dehydration two kinds reaction carries out generating isobutene reaction process simultaneously, and MTBE and TBA conversion ratio is high, selective isobutene is high.
The catalyst being only shell with unmodified aluminium oxide, itself MTBE and TBA conversion ratio is all not high, and the selectivity of isobutene. is also poor；Catalyst is prepared, although the conversion ratio of MTBE and TBA, selective isobutene increase, but still undesirable even if being mixed with amorphous silica-alumina by modified activated aluminum oxide.
Table 2 comparative example 3-4, the TBA fixing bed appreciation condition of cracking of embodiment 5,6 and result
| Comparative example 3 | Comparative example 3 | Comparative example 4 | Comparative example 4 | Embodiment 5 | Embodiment 6 | |
| Catalyst | DB-3 | DB-3 | DB-4 | DB-4 | SL-5 | SL-6 |
| Volume space velocity during TBA liquid, h-1 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Reaction temperature, DEG C | 265 | 210 | 265 | 210 | 210 | 210 |
| Reaction pressure, MPa | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
| TBA conversion ratio, wt% | 97.2 | 91.8 | 98.5 | 93.4 | 97.8 | 98.2 |
| The selectivity of isobutene., wt% | 92.5 | 93.5 | 84.3 | 83.8 | 98.8 | 99.7 |
As can be seen from Table 2, when activated alumina catalyst is for TBA cracking, reaction temperature is catalytic performance when 265 DEG C is catalytic performance when 210 DEG C significantly better than reaction temperature.Further, the aluminium oxide catalyst after stannum, Si modification is for TBA cracking reaction, the conversion ratio of TBA is improved, but selectivity is undesirable.
The fixing bed appreciation condition of MTBE cracking of table 3 comparative example 5 and result
| Comparative example 5 | Comparative example 5 | |
| Catalyst | DB-5 | DB-5 |
| Volume space velocity during MTBE liquid, h-1 | 2.5 | 2.0 |
| Volume space velocity during water liquid, h-1 | 0.1 | 0.1 |
| Reaction temperature, DEG C | 230 | 210 |
| Reaction pressure, MPa | Normal pressure | 0.05 |
| MTBE conversion ratio, wt% | 99.6 | 98.2 |
| The selectivity of isobutene., wt% | 99.2 | 99.3 |
As can be seen from Table 3, when amorphous silicon Al catalysts is for MTBE cracking, reaction temperature is catalytic performance when 230 DEG C is catalytic performance when 210 DEG C significantly better than reaction temperature.
The evaluation result of table 4 embodiment 5,6
| Catalyst | SL-5 | SL-6 |
| Volume space velocity during total liquid, h-1 | 3.0 | 3.0 |
| Volume space velocity during MTBE liquid, h-1 | 2.0 | 2.0 |
| Volume space velocity during TBA liquid, h-1 | 1.0 | 1.0 |
| Reaction temperature, DEG C | 210 | 210 |
| Reaction pressure, MPa | 0.05 | 0.05 |
| MTBE conversion ratio, wt% | 99.4 | 99.8 |
| TBA conversion ratio, wt% | 99.8 | 98.3 |
| Selective isobutene, wt% | 99.5 | 99.6 |
As can be seen from Table 4, do not adopt catalyst grating, individually adopt a kind of catalyst to carry out MTBE and TBA compound and prepare isobutene reaction, all do not reach the effect after table 1 grating of the present invention.
Claims (11)
1. the method that a MTBE and TBA compound prepares isobutene., contact to react with catalyst A and catalyst B successively including MTBE and TBA compound and prepare isobutene., catalyst A wherein used contains nucleocapsid structure component, core is amorphous silica-alumina, shell is the aluminium oxide by silicon and tin modification, it is wherein 1:18～1:3 by the weight ratio of the aluminium oxide of silicon and tin modification Yu amorphous silica-alumina, by in the aluminium oxide of silicon and tin modification, silicone content is 0.5wt%～2.0wt%, and Theil indices is 0.2wt%～1.0wt%；Catalyst B contains nucleocapsid structure component, core is amorphous silica-alumina, shell is the aluminium oxide by silicon and tin modification, it is wherein 1:60～1:20 by the weight ratio of the aluminium oxide of silicon and tin modification Yu amorphous silica-alumina, by in the aluminium oxide of silicon and tin modification, silicone content is 0.5wt%～2.0wt%, and Theil indices is 0.2wt%～1.0wt%.
2. in accordance with the method for claim 1, it is characterised in that: the admission space of catalyst A and catalyst B is than for 1:2～1:10, it is preferred to 1:3～1:5.
3. in accordance with the method for claim 1, it is characterised in that: in catalyst A, the weight ratio of the aluminium oxide of silicon and tin modification Yu amorphous silica-alumina it is 1:10～1:4；In catalyst B, the weight ratio of the aluminium oxide of silicon and tin modification Yu amorphous silica-alumina it is 1:30～1:50.
4. in accordance with the method for claim 1, it is characterised in that: catalyst A or in catalyst B, by the aluminium oxide of silicon and tin modification, silicone content is 0.8wt%～1.5wt%, and Theil indices is 0.3wt%～0.8wt%.
5. in accordance with the method for claim 1, it is characterised in that: catalyst A or in catalyst B, in described amorphous silica-alumina, SiO2Content is 60.0wt%～99.0wt%, Al2O3Content is 1.0wt%～40.0wt%, it is preferred to SiO2Content is 80.0wt%～95.0wt%, Al2O3Content is 5.0wt%～20.0wt%.
6. in accordance with the method for claim 1, it is characterised in that: catalyst A or in catalyst B, the character of described amorphous silica-alumina is as follows: specific surface area is 240m2/ g～450m2/ g, pore volume is 0.4mL/g～0.9mL/g.
7. the method described in claim 1 or 6, it is characterised in that: catalyst A or in catalyst B, described amorphous silica-alumina is to obtain after hydrothermal treatment, and wherein hydrothermal conditions is: temperature is 150 DEG C～450 DEG C, and the time is 5h～24h.
8. the method described in claim 1,5 or 6, it is characterized in that: catalyst A or in catalyst B, described amorphous silica-alumina is the amorphous silica-alumina containing activating agent, wherein activating agent is selected from one or more in group iia and group VIII metal, wherein group iia metal is one or more in Be, Mg and Ca, group VIII metal is one or more in Ni, Pd and Pt, with the weight of the amorphous silica-alumina containing activating agent for benchmark, the content that activating agent is counted with oxide is for 0.3wt%～2.0wt%.
9. in accordance with the method for claim 1, it is characterised in that: adopting fixed-bed process, the reaction condition adopted is: during total liquid, volume space velocity is 0.5h-1～10.0h-1, temperature is 120 DEG C～300 DEG C, and pressure is normal pressure～0.6MPa, it is preferred to during total liquid, volume space velocity is 2.0h-1～5.0h-1, temperature is 150 DEG C～250 DEG C；Pressure is normal pressure～0.3MPa.
10. in accordance with the method for claim 1, it is characterised in that: in the compound of MTBE and TBA, the weight ratio of MTBE and TBA is 1:1 ~ 40:1, it is preferred to 2:1 ~ 20:1.
11. in accordance with the method for claim 1, it is characterised in that: in the compound of MTBE and TBA, methyl sec-butyl ether≤0.2wt%, methanol≤0.05wt%, isobutylene oligomer≤0.05wt%, carbon four and carbon less than four hydro carbons≤0.1wt%.
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| CN108435221A (en) * | 2017-02-16 | 2018-08-24 | 四川润和催化新材料股份有限公司 | A kind of catalyst for dehydrogenation of low-carbon paraffin and its preparation method and application |
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| US5880324A (en) * | 1994-01-21 | 1999-03-09 | Intevep, S.A. | Catalyst for use in the dehydrogenation and isomerization of paraffins and method |
| CN1853772A (en) * | 2005-04-27 | 2006-11-01 | 中国石油化工股份有限公司 | Catalyst in preparation of isobutene by methyl tertbutyl ether pyrolysis |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108435221A (en) * | 2017-02-16 | 2018-08-24 | 四川润和催化新材料股份有限公司 | A kind of catalyst for dehydrogenation of low-carbon paraffin and its preparation method and application |
| CN108435221B (en) * | 2017-02-16 | 2020-12-18 | 润和催化材料(浙江)有限公司 | Low-carbon alkane dehydrogenation catalyst and preparation method and application thereof |
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| CN105712831B (en) | 2018-04-10 |
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