CN110496631A - The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane - Google Patents
The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane Download PDFInfo
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- CN110496631A CN110496631A CN201810475362.4A CN201810475362A CN110496631A CN 110496631 A CN110496631 A CN 110496631A CN 201810475362 A CN201810475362 A CN 201810475362A CN 110496631 A CN110496631 A CN 110496631A
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- dehydrogenation
- catalyst
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 272
- 239000003054 catalyst Substances 0.000 title claims abstract description 138
- 235000013847 iso-butane Nutrition 0.000 title claims abstract description 137
- 239000001282 iso-butane Substances 0.000 title claims abstract description 136
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 127
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000000741 silica gel Substances 0.000 claims abstract description 87
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 87
- 229960001866 silicon dioxide Drugs 0.000 claims abstract description 87
- 238000005406 washing Methods 0.000 claims abstract description 35
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 32
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001914 filtration Methods 0.000 claims abstract description 32
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 18
- 235000011187 glycerol Nutrition 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 238000001694 spray drying Methods 0.000 claims abstract description 12
- 238000012545 processing Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000009826 distribution Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 230000002902 bimodal effect Effects 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- -1 isobutyl Alkane Chemical class 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000005470 impregnation Methods 0.000 abstract description 9
- 239000000306 component Substances 0.000 description 66
- 239000000047 product Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
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- 230000000694 effects Effects 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 12
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 11
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 11
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
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- 101150116295 CAT2 gene Proteins 0.000 description 8
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 8
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 8
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- 239000006185 dispersion Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
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- 238000001179 sorption measurement Methods 0.000 description 5
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 238000007430 reference method Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000004876 x-ray fluorescence Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
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- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000004231 fluid catalytic cracking Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 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
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
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- 239000003595 mist Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-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
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 241001292396 Cirrhitidae Species 0.000 description 1
- 102100021202 Desmocollin-1 Human genes 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 1
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910017299 Mo—O Inorganic materials 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FAXVXGOUWBCEFQ-UHFFFAOYSA-N [C].CC(C)=C Chemical compound [C].CC(C)=C FAXVXGOUWBCEFQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- 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 catalyst field, the method for a kind of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane is disclosed.The method for preparing dehydrogenation of isobutane catalyst includes: that (a) contacts waterglass, inorganic acid solution, n-butanol and glycerine, then obtained product of contact is successively filtered washing, ball milling, slurrying and spray drying, obtains silica-gel carrier；(b) the silica obtained carrier of step (a) is subjected to impregnation in the solution containing Pt component presoma and Zn component presoma, then solvent processing and drying are successively removed, wherein, filtration washing described in step (a) carries out in purpose ceramic-film filter, and content of the sodium ion in terms of sodium element is not higher than 0.2 weight % in the material after filtration washing.The method is easy to operate, energy saving, environmental-friendly, in the case that gained dehydrogenation of isobutane catalyst noble metal load capacity is very low, can reach preferable catalytic activity and stability.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to a kind of method for preparing dehydrogenation of isobutane catalyst and by this
The method of the dehydrogenation of isobutane catalyst and preparing isobutene through dehydrogenation of iso-butane of method preparation.
Background technique
Isobutene is a kind of very important Organic Chemicals, mainly for the preparation of methyl tertiary butyl ether(MTBE), butyl rubber,
Methyl ethyl ketone, polyisobutene, methyl methacrylate, isoprene, tertiary butyl phenol, tert-butylamine, 1,4- butanediol and ABS resin etc. are each
Kind Organic Ingredients and fine chemicals.The main source of isobutene is that the by-product C4 of naphtha vapor cracking ethylene preparation device evaporates
Divide, the tertiary fourth of by-product in the by-product C 4 fraction of refinery's fluid catalytic cracking (FCC) device and the synthesis of Halcon method propylene oxide
Alcohol (TAB).
In recent years, with the development and utilization of isobutene downstream product, the demand of isobutene increases year by year, traditional isobutyl
Alkene production has been unable to meet chemical industry to the great demand of isobutene, therefore the research and development of isobutene production new technology
A big hot spot as chemical industry.Wherein, most competitive technology has dehydrogenation of isobutane, n-butene skeletal isomerization and new
Type FCC apparatus increases production isobutene.In these methods, the repercussion study of iso-butane direct dehydrogenation preparing isobutene is more early, has been carried out
Industrialized production.There is C4 resource abundant in China, but the chemical utilization rate of China's C 4 fraction is lower, and most of iso-butanes are straight
It connects and is used as fuel, waste is serious.Rationally utilizing C4 resource is the urgent task that petrochemical industry research field faces.Therefore,
Preparing isobutene through dehydrogenation of iso-butane has very big development prospect in China.
There are two main classes for the catalyst of preparing isobutene through dehydrogenation of iso-butane: oxide catalyst and noble metal catalyst.Oxidation
Object catalyst mainly includes Cr2O3、V2O5、Fe2O3、MoO3, ZnO etc. and their composite oxides V-Sb-O, V-Mo-O,
Ni-V-O, V-Nb-O, Cr-Ce-O, molybdate etc..Compared with noble metal catalyst, oxide catalyst is on the low side.But
Such catalyst is easy to carbon distribution, and catalytic activity, selectivity and stability are all relatively low.In addition, most oxide catalysts contain
The ingredient being more toxic, is unfavorable for environmental protection.Dehydrogenation reaction research on noble metal catalyst has had very long history, and other
Metal oxide catalyst is compared, and noble metal catalyst activity is higher, and selectivity is preferable, and to more environment-friendly.But
Lead to catalyst higher cost since noble metal is expensive, and the performance of such catalyst also has not been reached yet and is satisfied with journey
Degree.
In order to improve the reactivity worth of catalyst for preparing isobutene through dehydrogenation of iso-butane, researcher has done many work.Such as:
Preparation method by changing catalyst improves catalyst performance (Industrial Catalysis, 2014,22 (2): 148-153), passes through addition
Auxiliary agent improves catalyst stability (Catal.Today, 2000,55 (3): 213-223), improves catalysis by improving carrier property
Agent carbon accumulation resisting ability (chemistry of fuel journal, 2013,41 (12): 1481-1487).However, currently used carrier specific surface area
It is smaller, both it had been unfavorable for active metal component in the dispersion of carrier surface, and had also been unfavorable for the diffusion of raw material and product in reaction process.
Therefore, how to improve the reactivity worth of dehydrogenation of isobutane catalyst be one, preparing isobutene through dehydrogenation of iso-butane field urgently
Problem to be solved.
In the prior art, carrier of the silica gel as loaded catalyst can be used, using the common raw material being easy to get, in letter
It can obtain that specific surface area is larger, the biggish silica-gel carrier in aperture under easy operating condition.However, conventional silica gel removes impurity
Means be plate and frame type filter-press, however plate and frame type filter-press occupied area is larger, simultaneously as plate and frame type filter-press is interruption
Formula operation, low efficiency, operation room environment is poor, there is secondary pollution, further, since removal impurity effect is poor using filter cloth, gives up
Water can not regeneration, water source is extremely wasted in washing process, simultaneously because discharge waste water can not be handled, and causes environment
Pollution and secondary waste.
To further investigate synthesized silicon rubber, it is necessary to attempt it is different go deimpurity method, with push catalyst carrier and
Dehydrogenation of isobutane prepares the further development of isobutene industry.
Summary of the invention
The purpose of the invention is to overcome existing dehydrogenation of isobutane to urge, catalyst preparation process is complicated, preparation process is easy
In causing, environmental pollution, impurity effect is poor for removal, energy consumption is high, dehydrogenation of isobutane catalyst noble metal active component obtained point
Uneven, catalytic activity and the poor defect of stability are dissipated, provides a kind of method for preparing dehydrogenation of isobutane catalyst and by this
The method of the dehydrogenation of isobutane catalyst and preparing isobutene through dehydrogenation of iso-butane of method preparation, method provided by the present invention are easy to
Operation, low energy consumption, environmental-friendly and low in cost, and dehydrogenation of isobutane catalyst obtained by this method, in noble-metal-supported
In the case that amount is very low, it will be able to reach preferable dehydrogenation activity, selectivity, stability and anti-carbon.
To achieve the goals above, one aspect of the present invention provides a kind of method for preparing dehydrogenation of isobutane catalyst, the party
Method the following steps are included:
(a) waterglass, inorganic acid solution, n-butanol and glycerine are contacted, then by obtained product of contact according to
It is secondary to be filtered washing, ball milling, slurrying and spray drying, obtain silica-gel carrier；
(b) the silica obtained carrier of step (a) is carried out in the solution containing Pt component presoma and Zn component presoma
Then impregnation is successively removed solvent processing and drying,
Wherein, filtration washing described in step (a) carries out in purpose ceramic-film filter, in the material after filtration washing sodium from
Content of the son in terms of sodium element is not higher than 0.2 weight %.
Second aspect of the present invention provides a kind of dehydrogenation of isobutane catalyst prepared by preceding method.
Third aspect present invention provides a kind of method of preparing isobutene through dehydrogenation of iso-butane, which comprises in catalyst
In the presence of hydrogen, iso-butane is subjected to dehydrogenation reaction, wherein the catalyst is to be taken off by iso-butane prepared by preceding method
Hydrogen catalyst.
Carrier structure (including the physical structures such as specific surface area, Kong Rong, pore-size distribution and the surface acidity of noble metal catalyst
The chemical structures such as position, Electronic Performance) not only the dispersion degree of active metal component is had a major impact, but also directly affect reaction
Mass transfer and diffusion in the process.Therefore, the catalytic performances such as activity, selectivity and stability of heterogeneous catalyst both depend on activity
The catalytic characteristics of component, but it is related with the feature of catalyst carrier.In order to reduce the bullion content in catalyst as far as possible, simultaneously
The activity and stability of catalyst are improved, the preparation process of carrier is most important.Most of commercially active oxidation aluminium surface hydroxyl
Base is excessive, acid too strong.It the use of this kind of aluminium oxide is that carrier prepares dehydrogenation, catalyst surface is easy to during the reaction
Carbon distribution, and then lead to fast deactivation.
The present inventor is by the study found that be filtered washing using purpose ceramic-film filter, using cross-flow filtration,
Crossflow velocity with higher in filter process, it is possible to reduce accumulation of the pollutant in film surface, membrane flux with higher are preceding
The product of contact of waterglass, inorganic acid solution, n-butanol and glycerine that phase is prepared directly is carried out with the state of mobile phase
Filtration washing removal of impurities, dust removal rate is high, low energy consumption, environmental-friendly, process is simple, and the waste water that cleans can regenerate recycling.
In addition, it is finer and smoother using the slurry that ball grinding technique and spray drying technology can make, it is obtained after being spray-dried
Spheroidal particle stable structure, can be recycled as catalyst carrier, intensity height is non-breakable.Using spray drying skill
Art, the partial size of obtained silica-gel carrier is small, particle diameter distribution is uniform and grading curve is narrow, can be to avoid carrying in use
Body is reunited, its mobility is improved, to catalyst obtained storage, transport, post-processing and application bring convenience.
Compared with prior art, the method provided by the present invention for preparing dehydrogenation of isobutane catalyst has the advantage that
(1) method provided by the present invention for preparing dehydrogenation of isobutane catalyst uses cross-flow filtration, higher due to having
Crossflow velocity reduces pollutant in the accumulation of film surface, improves the flux of film, filtration washing process dust removal rate is high, removes
Miscellaneous process is simple, and corollary apparatus is few, and low energy consumption, and experimental provision cleaning is simple, can back flush, power of regeneration is strong；
(2) the method preparation process provided by the present invention for preparing dehydrogenation of isobutane catalyst is simple, and condition is easily controllable,
Good repetitiveness；
(3) the dehydrogenation of isobutane catalyst of method preparation provided by the present invention can be in main active component (i.e. your gold
Belong to) in the case that load capacity is very low, it will be able to reach preferable dehydrogenation activity, selectivity, stability and anti-carbon, Neng Gouyou
Effect reduces the preparation cost of dehydrogenation of isobutane catalyst；
(4) in the dehydrogenation of isobutane catalyst of method preparation provided by the present invention, the center Zn of structure oxidation is in high temperature
Reducing condition stability inferior is very high, can inhibit the inactivation of carrier loaded single Pt component, reduces carbon distribution, and effectively neutralizes and carry
The strong acid center in body surface face keeps carrier surface no acidic, and the dispersion degree of Pt component is improved by geometric effect, so as to aobvious
Write the carbon distribution risk reduced in iso-butane anaerobic dehydrogenation preparing isobutene reaction process, the selectivity and isobutyl for improving purpose product
The stability of alkane dehydrogenation；
(5) on the dehydrogenation of isobutane catalyst of method provided by the present invention preparation noble metal active component dispersion degree compared with
Height, and then guarantee that iso-butane catalyst is not easy to inactivate because active metal particles are reunited during the reaction；
(6) the dehydrogenation of isobutane catalyst of method preparation provided by the present invention is used for iso-butane anaerobic dehydrogenation preparing isobutene
Good catalytic performance is shown when reaction, iso-butane high conversion rate, selective isobutene is high, and catalyst stability is good, resistance to
Sour, alkaline-resisting, organic solvent-resistant, carbon deposition quantity is low in catalytic process.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the SEM scanning electron microscope (SEM) photograph of the silica-gel carrier of embodiment 1；
Fig. 2 is the pore size distribution curve of the silica-gel carrier of embodiment 1.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
As previously mentioned, the first aspect of the present invention provides a kind of method for preparing dehydrogenation of isobutane catalyst, this method
The following steps are included:
(a) waterglass, inorganic acid solution, n-butanol and glycerine are contacted, then by obtained product of contact according to
It is secondary to be filtered washing, ball milling, slurrying and spray drying, obtain silica-gel carrier；
(b) the silica obtained carrier of step (a) is carried out in the solution containing Pt component presoma and Zn component presoma
Then impregnation is successively removed solvent processing and drying,
Wherein, filtration washing described in step (a) carries out in purpose ceramic-film filter, in the material after filtration washing sodium from
Content of the son in terms of sodium element is not higher than 0.2 weight %.
According to the present invention, the purpose ceramic-film filter is a set of accurate super mistake that can be widely applied to various fields
Cleaning equipment is filtered, core component is micropore ceramics membrane filter tube, it is that plurality of raw materials carry out section is waited until with kaolin, zirconium oxide
Formula is learned, a kind of mesh-structured microfiltration membranes of solid is formed through processes such as biscuiting, crushing, classification, molding, pore-creating, films, has
Excellent thermal stability and hole stability, not only intensity is high and resistant to chemical etching, is suitable for the secondary filter of various media,
Cleaning and regeneration performance is good, has both the two-fold advantage of high efficiency filter and secondary filter, can filter under 5-10m/s filtering velocity.
According to the present invention, the filtration washing in step (a) carries out in purpose ceramic-film filter, and the filtration washing is a kind of
The fluid separation process of " cross-flow filtration " form, specifically, the separation process include: by waterglass, inorganic acid solution, n-butanol
With the product of contact of glycerine directly with the state of mobile phase in membrane tube flow at high speed, according in certain membrane aperture range
Interior, then permeability is different for the material molecule diameter difference of infiltration, and using the pressure difference of film two sides as driving force, film is filter medium,
Under certain pressure driving effect, clarified permeation liquid (water, inorganic salts Na containing small molecule component+, the small molecules such as surfactant
Liquid) along direction normal thereto film is penetrated outward, muddy concentrate (suspended matter, glue and microorganism containing macromolecular components
Equal macromolecular substances) be blocked on film by modes such as mechanical filter, absorption outer surface or inner surface with filtration time
Extending, filtration resistance also increases on year-on-year basis, when pressure difference, which reaches, presets blowback pressure difference, motor drive and each in backwash mechanism
Respective valves starting, is run by program switch, and compressed air can be used in backwash or water is completed, and can also use purified liquid
Or solvent is realized, so that the fluid is achieved the purpose that separation, concentration, purifying.In the present invention, the filtration washing process exists
It is carried out under 5-10m/s filtering velocity, entire filtration washing process needs to be continuously replenished cleaning solution, and the mode of the washing can be washing
And/or alcohol is washed, such as can first be washed repeatedly with deionized water and backwash, then is washed repeatedly with ethyl alcohol and backwash,
To reduce pollutant in the viscous glutinous accumulation of film surface, membrane flux is improved, respective washing times and number of backwashes can be according to realities
The experiment effect on border is selected, until content of the sodium ion in terms of sodium element is not higher than in the material in membrane tube after filtration washing
0.2 weight %, preferably 0.01-0.03 weight % finally collect the mixed material in membrane tube, to subsequent processing, entire load
The preparation process of body is easy to operate, energy saving, and when being filtered washing using purpose ceramic-film filter, without artificial online
Operation, it is time saving and energy saving.
In addition, being sprayed present invention employs the slurry that ball grinding technique and spray drying technology make is finer and smoother
The silica-gel carrier stable structure obtained after mist is dry, can recycle, intensity height is non-breakable as catalyst carrier.Using
Spray drying technology, the partial size of obtained silica-gel carrier is small, particle diameter distribution is uniform and grading curve is narrow, can be to avoid making
Reunited with carrier in the process, improve its mobility, for follow-up storage, transport, post-processing and application bring convenience.Finally
Obtained silica-gel carrier specific surface area and aperture are larger, are conducive to noble metal component in the fine dispersion of carrier surface, so that system
Standby catalyst is in the case where noble-metal-supported amount is very low, it will be able to reach preferable dehydrogenation activity, selectivity, stability and
Anti-carbon.
In the forming process of above-mentioned dehydrogenation of isobutane catalyst, raw material when mainly preparing silica-gel carrier by control is used
Amount than and reaction condition the pore-size distribution of the carrier control as bimodal distribution, and pass through control forming method (that is, first by
Waterglass, inorganic acid solution, the material that the product of contact filtration washing of n-butanol and glycerine obtains carry out ball milling, then will
To solid powder water slurrying after be spray-dried) by the control of the microscopic appearance of the silica-gel carrier of the bimodal distribution be spherical shape.
According to the present invention, in step (a), the condition that the waterglass is contacted with inorganic acid is preferably included: temperature 10-
60 DEG C, more preferably 20-40 DEG C；Time is 1-5h, more preferably 1.5-3h, pH value 2-4.In order to increase the silica gel of preparation
Aperture size, it is preferable that the waterglass, inorganic acid solution, n-butanol and glycerine dosage weight ratio be 3-6:1:
0.8-2.5:0.8-2.5, it is highly preferred that the weight ratio of dosage of the waterglass, inorganic acid solution, n-butanol and glycerine is
3-6:1:1:1.In order to be more advantageous to the uniform mixing between each substance, the waterglass, inorganic acid solution, n-butanol and glycerine
Contact preferably carry out under agitation.
According to the present invention, in step (a), the waterglass is the aqueous solution of the sodium metasilicate of this field routine, concentration
It can be 10-50 weight %, preferably 12-30 weight %.
According to the present invention, in step (a), the inorganic acid can be one of sulfuric acid, nitric acid and hydrochloric acid or a variety of.
The inorganic acid can use in pure form, can also be used in the form of its aqueous solution.The dosage of the inorganic acid is excellent
Choosing is so that the pH value of the contact conditions reaction system of waterglass and inorganic acid is 2-4.
According to the present invention, in step (a), the object of the ball milling be by purpose ceramic-film filter filtration washing to sodium from
Content of the son in terms of sodium element is not higher than 0.2 weight %, crosses diafiltration preferably in the ceramic filtering membrane tube of 0.01-0.03 weight %
Product is washed, the concrete operation method and condition of the ball milling are not particularly limited, and are carried not destroy or not destroy silica gel substantially
Subject to the structure of body.Those skilled in the art can select various suitable conditions to implement the present invention according to mentioned above principle.Tool
Body, the ball milling can carry out in the ball mill, wherein the diameter of abrading-ball can be 2-3mm in ball mill；The quantity of abrading-ball
It can reasonably be selected according to the size of ball grinder, the ball grinder for being 50-150mL for size usually can be used 1
Abrading-ball；The material of the abrading-ball can be agate, polytetrafluoroethylene (PTFE) etc., preferably agate.The condition of the ball milling includes: abrading-ball
Revolving speed can be 300-500r/min, the temperature in ball grinder can be 15-100 DEG C, and the time of ball milling can be 0.1-100
Hour.
According to the present invention, in step (a), the concrete operation method and condition of the spray drying are the routine of this field
Selection.Specifically, by by after the ball milling product and the slurry that is made into of water be added in atomizer high speed rotation to realize spray
Mist is dry.Wherein, the condition of the spray drying, which includes: temperature, to be 100-300 DEG C, and the revolving speed of rotation can be 10000-
15000r/min；Under preferable case, the condition of the spray drying includes: that temperature is 150-250 DEG C, and the revolving speed of rotation is
11000-13000r/min；Under most preferred case, the condition of the spray drying includes: that temperature is 200 DEG C, and the revolving speed of rotation is
12000r/min。
According to the present invention, in step (b), the silica-gel carrier carried metal component can using dipping by the way of, according to
Capillary pressure by the cellular structure of the carrier enters metal component in the duct of the silica-gel carrier, while metal component
It can also be in the adsorption of the silica-gel carrier, until metal component reaches adsorption equilibrium on the surface of the carrier.The leaching
Stain processing can be handled for co-impregnation, or step impregnation processing.In order to save preparation cost, simplify experimental technique, institute
Stating impregnation is preferably co-impregnation processing；It is further preferred that the condition of the co-impregnation processing includes: that silica-gel carrier exists
Solution containing Pt component presoma and Zn component presoma is mixed, and the temperature of the dipping can be 25-50 DEG C,
The time of the dipping can be 2-6h.
According to the present invention, in step (b), the Pt component presoma is preferably H2PtCl6, the Zn component presoma
Preferably Zn (NO3)2。
There is no particular limitation for concentration of the present invention to the solution containing Pt component presoma and Zn component presoma,
It can be the conventional selection of this field, for example, the concentration of the Pt component presoma can be 0.001-0.003mol/L, it is described
The concentration of Zn component presoma can be 0.015-0.1mol/L.
According to the present invention in step (b), the dosage of the silica-gel carrier, Pt component presoma and Zn component presoma makes
In the dehydrogenation of isobutane catalyst that must be prepared, on the basis of the total weight of the dehydrogenation of isobutane catalyst, the silica-gel carrier
Content be 98-99.4 weight %, content of the Pt component in terms of Pt element be 0.1-0.5 weight %, the Zn component with
The content of Zn element meter is 0.5-1.5 weight %.
Under preferable case, the dosage of the silica-gel carrier, Pt component presoma and Zn component presoma makes the different of preparation
In butane dehydrogenation catalyst, on the basis of the total weight of the dehydrogenation of isobutane catalyst, the content of the silica-gel carrier is
98.4-99 weight %, content of the Pt component in terms of Pt element are 0.2-0.4 weight %, and the Zn component is in terms of Zn element
Content be 0.8-1.2 weight %.
According to the present invention, the process of the removal solvent processing can adopt with the conventional methods in the field, such as can adopt
With the solvent in Rotary Evaporators removal system.
According to the present invention, in step (b), the drying can carry out in drying box, and the condition of the drying can be with
Include: temperature be 110-150 DEG C, time 3-6h.
Second aspect of the present invention provides the dehydrogenation of isobutane catalyst prepared by preceding method.
According to the present invention, the dehydrogenation of isobutane catalyst include carrier and load Pt component on the carrier and
Zn component, wherein the carrier is silica-gel carrier, and the average grain diameter of the silica-gel carrier is 20-60 μm, and specific surface area is
300-600m2/ g, pore volume 0.1-2.5mL/g, pore-size distribution are bimodal distribution, and the bimodal corresponding most probable pore size
Respectively 1-4.5nm and 20-50nm.
According to the present invention, in the dehydrogenation of isobutane catalyst, the average grain diameter of the silica-gel carrier uses laser particle size
Distribution instrument measures, and specific surface area, pore volume and most probable pore size are measured according to nitrogen adsorption methods.
According to the present invention, the silica-gel carrier by by structural parameter control within above range, it can be ensured that it is described
Silica-gel carrier is not susceptible to reunite, and dehydrogenation of isobutane system can be improved in the loaded catalyst as made from the silica-gel carrier
Reaction raw materials conversion ratio during isobutene reaction.When the specific surface area of the silica-gel carrier is less than 300m2/ g and/or hole body
When product is less than 0.1mL/g, the catalytic activity for the loaded catalyst being made from it can be significantly reduced；When the ratio of the silica-gel carrier
Surface area is greater than 600m2When/g and/or pore volume are greater than 2.5mL/g, the loaded catalyst being made from it is in dehydrogenation of isobutane
Reunion is easy to happen in preparing isobutene reaction process, to influence the reaction raw materials in preparing isobutene through dehydrogenation of iso-butane reaction process
Conversion ratio.
In the preferred case, the average grain diameter of the silica-gel carrier is 20-50 μm, specific surface area 350-450m2/
G, pore volume 0.6-2mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 1.5-
4.2nm and 25-48nm.
According to the present invention, on the basis of the total weight of the dehydrogenation of isobutane catalyst, the content of the carrier is 98-
99.4 weight %, content of the Pt component in terms of Pt element are 0.1-0.5 weight %, Zn component the containing in terms of Zn element
Amount is 0.5-1.5 weight %.
Under preferable case, on the basis of the total weight of the dehydrogenation of isobutane catalyst, the content of the carrier is 98.4-
99 weight %, content of the Pt component in terms of Pt element are 0.2-0.4 weight %, content of the Zn component in terms of Zn element
For 0.8-1.2 weight %.
It is further preferred that the average grain diameter of the dehydrogenation of isobutane catalyst is 20-50 μm, specific surface area is
320-420m2/ g, pore volume 0.5-1.8mL/g, pore-size distribution are bimodal distribution, and the bimodal corresponding most probable pore size
Respectively 1.2-4nm and 22-45nm.
According to the present invention, the silica-gel carrier can be prepared according to method above-mentioned.
As previously mentioned, the third aspect of the present invention provides a kind of method of preparing isobutene through dehydrogenation of iso-butane, the method
It include: that iso-butane is subjected to dehydrogenation reaction in the presence of catalyst and hydrogen, wherein the catalyst is by preceding method
The dehydrogenation of isobutane catalyst of preparation.
When the dehydrogenation of isobutane catalyst of method preparation provided by the present invention is used for catalyzing iso-butane alkane dehydrogenation preparing isobutene,
The selectivity of the conversion ratio and isobutene that can make iso-butane, which has, greatly to be improved.
According to the present invention, in order to improve iso-butane conversion ratio and prevent the catalyst coking, under preferable case, iso-butane
Dosage and hydrogen dosage molar ratio be 0.5-1.5:1.
There is no particular limitation for condition of the present invention to the dehydrogenation reaction, can be the conventional selection of this field, for example,
The condition of the dehydrogenation reaction may include: that reaction temperature is 550-650 DEG C, reaction pressure 0.05-0.2MPa, the reaction time
For 20-40h, iso-butane mass space velocity is 2-5h-1。
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, filtration washing is in the alumina ceramic membrane filtering purchased from my long company of Nanjing
It is carried out in device；X-ray diffractometer of the X-ray diffraction analysis in the model D8Advance purchased from Bruker AXS company, Germany
Upper progress；Scanning electron microscope analysis carries out in the scanning electron microscope purchased from the model XL-30 of FEI Co., the U.S.；Kong Jie
Structure Parameter analysis carries out on the ASAP2020-M+C type adsorption instrument purchased from the production of U.S. Micromeritics company, sample
Specific surface area and pore volume, which calculate, uses BET method；The particle diameter distribution of sample carries out on Malvern laser particle analyzer；Rotation is steamed
Instrument is sent out as the production of IKA company, Germany, model RV10digital；The activity component load quantity of dehydrogenation of isobutane catalyst is being purchased
It is measured from the wavelength dispersion X-ray fluorescence spectrometer that Dutch Panaco company model is Axios-Advanced；Reaction product
The analysis of ingredient carries out on the gas chromatograph purchased from agilent company model 7890A.
In following EXPERIMENTAL EXAMPLE and Experimental comparison's example, conversion ratio (%)=reaction consumption iso-butane of iso-butane
Amount/iso-butane primary quantity × 100%；
Amount/iso-butane total flow of the selectivity (%) of isobutene=generation isobutene consumption iso-butane ×
100%.
Embodiment 1
The present embodiment is for illustrating dehydrogenation of isobutane catalyst and preparation method thereof.
(1) preparation of silica-gel carrier
By waterglass that concentration is 15 weight %, sulfuric acid solution, n-butanol and glycerine that concentration is 12 weight % with weight
Amount is 3 with the sulfuric acid adjustment pH that concentration is 98 weight % than carrying out mixing and the haptoreaction 1.5h at 30 DEG C for 5:1:1:1,
Obtain product of contact A1.The product of contact A1 is passed through in ceramic membrane filter system and uses deionized water and ethyl alcohol filtration washing,
Being washed till content of the sodium ion in terms of sodium element in material is 0.02 weight %, then collects the washed product in ceramic filtering membrane tube
B1 takes washed product B1 described in 30g to be put into 100ml ball grinder, wherein the material of ball grinder is polytetrafluoroethylene (PTFE), abrading-ball material
Matter is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 400r/min.Ball grinder is closed, temperature is in ball grinder
Ball milling 5 hours at 60 DEG C, obtain 30g solid powder；The solid powder is dissolved in 30g deionized water and is made into slurry, later
It is spray-dried at 200 DEG C in the case where revolving speed is 12000r/min, obtains 30g and carried with the spherical silica gel of bimodal distribution aperture structure
Body C1.In the preparation process of the spherical silica gel support C 1, one ton of silica-gel carrier C1 is obtained, the ceramic membrane mistake is used
Filter system is filtered washing needs and exhausts totally three tons of ionized water and ethyl alcohol.
(2) preparation of dehydrogenation of isobutane catalyst
By 0.080g H2PtCl6·6H2O and 0.457g Zn (NO3)2·6H2O is dissolved in 100ml deionized water, is mixed
The spherical silica gel support C 1 that 10g step (1) is prepared is immersed in the mixture solution, at 25 DEG C by polymer solution
After impregnating 5h, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product, it is 120 that solid product, which is placed in temperature,
DEG C drying box in, dry 3h obtains dehydrogenation of isobutane catalyst Cat-1 and (is obtained by x-ray fluorescence analysis, described different
In butane dehydrogenation catalyst Cat-1, on the basis of the total weight of dehydrogenation of isobutane catalyst Cat-1, Pt component is in terms of Pt element
Content be content of 0.3 weight %, the Zn component in terms of Zn element be 1 weight %, remaining is carrier).
Spherical silica gel support C 1 and dehydrogenation of isobutane catalyst Cat-1 are carried out with XRD, scanning electron microscope and nitrogen adsorption instrument
Characterization.
Fig. 1 is the SEM scanning electron microscope (SEM) photograph of the spherical silica gel support C 1, as seen from the figure, the spherical silica gel support C 1
Microscopic appearance is the spheric granules that granularity is 20-60 μm, and its good dispersion property.
Fig. 2 is the pore size distribution curve figure of the spherical silica gel support C 1, it can be seen from the figure that the spherical silica gel carries
The pore-size distribution of body C1 is bimodal distribution, and duct is highly uniform.
Table 1 is the pore structure parameter of spherical silica gel support C 1 and dehydrogenation of isobutane catalyst Cat-1.
Table 1
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Partial size (μm) |
| Silica-gel carrier C1 | 390 | 2 | 3.2,37.5 | 40 |
| Catalyst Cat-1 | 355 | 1.5 | 2.2,31.4 | 40 |
*: the first most probable pore size and the second most probable pore size are separated with comma: being successively according to sequence from left to right
One most probable pore size and the second most probable pore size.
By spherical silica gel support C 1 it can be seen from the data of table 1 after supporting Pt component and Zn component, specific surface area and
Pore volume is reduced, and for this explanation during load-reaction, Pt component and Zn component enter spherical silica gel support C 1
It is internal.
Comparative example 1
This comparative example is for illustrating dehydrogenation of isobutane catalyst of reference and preparation method thereof.
Carrier and dehydrogenation of isobutane catalyst are prepared according to the method for embodiment 1, it is different, in the process for preparing silica gel
In, the product of contact A1 is filtered, and the content being washed with deionized to sodium ion in terms of sodium element is 0.02 weight
% is measured, silica gel filter cake DB1 is obtained, is then filtered washing without ceramic filtration membrane filter, be directly placed into ball grinder and carry out
Ball milling is then dried, to respectively obtain spherical silica gel carrier D1 and dehydrogenation of isobutane catalyst Cat-D-1.
Comparative example 2
This comparative example is for illustrating dehydrogenation of isobutane catalyst of reference and preparation method thereof.
Carrier and dehydrogenation of isobutane catalyst are prepared according to the method for embodiment 1, it is different, in the process for preparing silica gel
In, be not added n-butanol and glycerine, but by waterglass and concentration that concentration is 15 weight % be 12 weight % sulfuric acid it is molten
Liquid is that 5:1 carries out mixing and the haptoreaction 1.5h at 30 DEG C with weight ratio, is then adjusted with the sulfuric acid that concentration is 98 weight %
Then pH value is filtered obtained reaction mass using plate and frame type filter-press to 3, then filters plate and frame type filter-press
The silica gel arrived is calcined 10 hours for 400 DEG C under nitrogen protection, with eliminating hydroxide and Residual water, to obtain the plate through thermal activation
The silica gel filter cake DB2 of frame filter press preparation.In silica gel filter cake DB2 preparation process, obtaining one ton of silica gel filter cake DB2 is needed
Want 11 tons of water consumption.Then the spherical silica gel support C 1 is substituted using the silica gel filter cake DB2 of identical weight part carry out Pt
The dip loading of component and Zn component, to respectively obtain silica-gel carrier D2 and dehydrogenation of isobutane catalyst Cat-D-2.
Comparative example 3
This comparative example is for illustrating dehydrogenation of isobutane catalyst of reference and preparation method thereof.
Carrier and dehydrogenation of isobutane catalyst are prepared according to the method for embodiment 1, it is different, use commercially available ES955
Silica gel (is purchased from U.S. Grace company, average grain diameter is 20-50 μm, specific surface area 250m2/ g, pore volume 1.5mL/
G, pore-size distribution are Unimodal Distribution, most probable pore size 15nm) it is used as carrier, then use the ES955 of identical weight part
Silica gel substitutes the dip loading that the spherical silica gel support C 1 carries out Pt component and Zn component, to respectively obtain ES955 silica gel
Carrier D3 and dehydrogenation of isobutane catalyst Cat-D-3.
Comparative example 4
This comparative example is for illustrating dehydrogenation of isobutane catalyst of reference and preparation method thereof.
Carrier and dehydrogenation of isobutane catalyst are prepared according to the method for embodiment 1, it is different, preparing dehydrogenation of isobutane
In the dipping process of catalyst, Zn (NO is not added3)2·6H20.080gH is only added in O2PtCl6·6H2O passes through co-impregnation
Only single Pt component is supported on silica-gel carrier, so that dehydrogenation of isobutane catalyst Cat-D-4 be made, is urged with dehydrogenation of isobutane
On the basis of the total weight of agent Cat-D-4, content of the Pt component in terms of Pt element is 0.3 weight %, remaining is carrier).
Embodiment 2
The present embodiment is for illustrating dehydrogenation of isobutane catalyst and preparation method thereof.
(1) preparation of silica-gel carrier
By waterglass that concentration is 15 weight %, sulfuric acid solution, n-butanol and glycerine that concentration is 12 weight % with weight
Amount is 2 with the sulfuric acid adjustment pH that concentration is 98 weight % than carrying out mixing and the haptoreaction 1.5h at 40 DEG C for 4:1:1:1,
Obtain product of contact A2.The product of contact A2 is passed through in ceramic membrane filter system and uses deionized water filtration washing, is washed till object
Content of the sodium ion in terms of sodium element is 0.01 weight % in material, then collects the washed product B2 in ceramic filtering membrane tube, takes 30g
The washed product B2 is put into 100ml ball grinder, wherein and the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate,
The diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 400r/min.Ball grinder is closed, temperature is ball at 80 DEG C in ball grinder
Mill 0.5 hour, obtains 30g solid powder；The solid powder is dissolved in 30g deionized water and is made into slurry, later at 250 DEG C
Under revolving speed be 11000r/min under be spray-dried, obtain 35g have bimodal distribution aperture structure spherical silica gel support C 2.In
In the preparation process of the spherical silica gel support C 2, one ton of silica-gel carrier C2 is obtained, the ceramic membrane filter system is used
It is filtered washing needs and exhausts four tons of ionized water.
(2) preparation of dehydrogenation of isobutane catalyst
By 0.080g H2PtCl6·6H2O and 0.457g Zn (NO3)2·6H2O is dissolved in 100ml deionized water, is mixed
The spherical silica gel support C 2 that 10g step (1) is prepared is immersed in the mixture solution, at 25 DEG C by polymer solution
After impregnating 5h, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product, it is 120 that solid product, which is placed in temperature,
DEG C drying box in, dry 3h obtains dehydrogenation of isobutane catalyst Cat-2 and (is obtained by x-ray fluorescence analysis, described different
In butane dehydrogenation catalyst Cat-2, on the basis of the total weight of dehydrogenation of isobutane catalyst Cat-2, Pt component is in terms of Pt element
Content be content of 0.3 weight %, the Zn component in terms of Zn element be 1 weight %, remaining is carrier).
Table 2 is the pore structure parameter of spherical silica gel support C 2 and dehydrogenation of isobutane catalyst Cat-2.
Table 2
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Partial size (μm) |
| Silica-gel carrier C2 | 385 | 1.8 | 3,45 | 45 |
| Catalyst Cat-2 | 356 | 1.2 | 2.1,36.5 | 45 |
*: the first most probable pore size and the second most probable pore size are separated with comma: being successively according to sequence from left to right
One most probable pore size and the second most probable pore size.
By spherical silica gel support C 2 it can be seen from the data of table 2 after supporting Pt component and Zn component, specific surface area and
Pore volume is reduced, and for this explanation during load-reaction, Pt component and Zn component enter spherical silica gel support C 2
It is internal.
Embodiment 3
The present embodiment is for illustrating dehydrogenation of isobutane catalyst and preparation method thereof.
(1) preparation of silica-gel carrier
By waterglass that concentration is 15 weight %, sulfuric acid solution, n-butanol and glycerine that concentration is 12 weight % with weight
Amount is 4 with the sulfuric acid adjustment pH that concentration is 98 weight % than carrying out mixing and the haptoreaction 1.5h at 20 DEG C for 6:1:1:1,
Obtain product of contact A3.The product of contact A3 is passed through in ceramic membrane filter system and uses deionized water and ethyl alcohol filtration washing,
Being washed till content of the sodium ion in terms of sodium element in material is 0.03 weight %, then collects the washed product in ceramic filtering membrane tube
B3 takes washed product B3 described in 30g to be put into 100ml ball grinder, wherein the material of ball grinder is polytetrafluoroethylene (PTFE), abrading-ball material
Matter is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 400r/min.Ball grinder is closed, temperature is in ball grinder
Ball milling 10 hours at 40 DEG C, obtain 30g solid powder；The solid powder is dissolved in 30g deionized water and is made into slurry, later
It is spray-dried at 250 DEG C in the case where revolving speed is 13000r/min, obtains 35g and carried with the spherical silica gel of bimodal distribution aperture structure
Body C3.In the preparation process of the spherical silica gel support C 3, one ton of silica-gel carrier C3 is obtained, the ceramic membrane mistake is used
Filter system is filtered washing needs and exhausts totally three tons of ionized water and ethyl alcohol.
(2) preparation of dehydrogenation of isobutane catalyst
By 0.080g H2PtCl6·6H2O and 0.457g Zn (NO3)2·6H2O is dissolved in 100ml deionized water, is mixed
The spherical silica gel support C 3 that 10g step (1) is prepared is immersed in the mixture solution, at 25 DEG C by polymer solution
After impregnating 5h, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product, it is 120 that solid product, which is placed in temperature,
DEG C drying box in, dry 3h obtains dehydrogenation of isobutane catalyst Cat-3 and (is obtained by x-ray fluorescence analysis, described different
In butane dehydrogenation catalyst Cat-3, on the basis of the total weight of dehydrogenation of isobutane catalyst Cat-2, Pt component is in terms of Pt element
Content be content of 0.3 weight %, the Zn component in terms of Zn element be 1 weight %, remaining is carrier).
Table 3 is the pore structure parameter of spherical silica gel support C 3 and dehydrogenation of isobutane catalyst Cat-3.
Table 3
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Partial size (μm) |
| Silica-gel carrier C3 | 380 | 1.7 | 2.8,38.6 | 50 |
| Catalyst Cat-3 | 351 | 1.4 | 2,32. | 50 |
*: the first most probable pore size and the second most probable pore size are separated with comma: being successively according to sequence from left to right
One most probable pore size and the second most probable pore size.
By spherical silica gel support C 3 it can be seen from the data of table 3 after supporting Pt component and Zn component, specific surface area and
Pore volume is reduced, and for this explanation during load-reaction, Pt component and Zn component enter spherical silica gel support C 3
It is internal.
EXPERIMENTAL EXAMPLE 1
The present embodiment is used to illustrate the method using dehydrogenation of isobutane catalyst preparation isobutene of the invention
0.5g dehydrogenation of isobutane catalyst Cat-1 is fitted into fixed-bed quartz reactor, control reaction temperature is 590
DEG C, reaction pressure 0.1MPa, iso-butane: the molar ratio of hydrogen is 1:1, and the reaction time is for 24 hours that iso-butane mass space velocity is
4h-1.Through Al2O3The reaction product of-S molecular sieve column separation is directly entered the Agilent 7890A gas equipped with hydrogen flame detector (FID)
Chromatography carries out on-line analysis, obtains iso-butane conversion ratio and selective isobutene is as shown in table 4.It uses after reaction
Carbon deposition quantity in the TGA/DSC1 thermogravimetric analyzer measurement dehydrogenation of isobutane catalyst Cat-1 of METTLER-TOLEDO company, such as
Shown in table 4.
EXPERIMENTAL EXAMPLE 2-3
Preparing isobutene through dehydrogenation of iso-butane is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, it is de- that iso-butane is respectively adopted
Hydrogen catalyst Cat-2 and dehydrogenation of isobutane catalyst Cat-3 replaces dehydrogenation of isobutane catalyst Cat-1.It is iso-butane conversion ratio, different
The carbon deposition quantity of butylene selectivity and dehydrogenation of isobutane catalyst is as shown in table 4.
Experimental comparison's example 1-4
Preparing isobutene through dehydrogenation of iso-butane is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, it is de- that iso-butane is respectively adopted
Hydrogen catalyst Cat-D-1~Cat-D-4 replaces dehydrogenation of isobutane catalyst Cat-1.Iso-butane conversion ratio, selective isobutene and
The carbon deposition quantity of dehydrogenation of isobutane catalyst is as shown in table 4.
Table 4
| Dehydrogenation | Iso-butane conversion ratio | Selective isobutene | Carbon deposition quantity of catalyst | |
| EXPERIMENTAL EXAMPLE 1 | Cat-1 | 36% | 95% | 0.8wt% |
| EXPERIMENTAL EXAMPLE 2 | Cat-2 | 33.5% | 94.2% | 1.1wt% |
| EXPERIMENTAL EXAMPLE 3 | Cat-3 | 34.2% | 94.4% | 1wt% |
| Experimental comparison's example 1 | Cat-D-1 | 20.2% | 72.6% | 5.5wt% |
| Experimental comparison's example 2 | Cat-D-2 | 18.5% | 63.5% | 5.7wt% |
| Experimental comparison's example 3 | Cat-D-3 | 12.6% | 62.1% | 6.2wt% |
| Experimental comparison's example 4 | Cat-D-4 | 8.5% | 55.7% | 5.8wt% |
From table 4, it can be seen that the dehydrogenation of isobutane catalyst prepared using silica-gel carrier of the invention is de- for iso-butane
When hydrogen preparing isobutene reacts, after reaction 24 hours, still available higher iso-butane conversion ratio and selective isobutene are said
Bright dehydrogenation of isobutane catalyst of the invention not only has preferable catalytic performance, but also stability is good, and carbon deposition quantity is low.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of method for preparing dehydrogenation of isobutane catalyst, which is characterized in that method includes the following steps:
(a) waterglass, inorganic acid solution, n-butanol and glycerine are contacted, then by obtained product of contact successively into
Row filtration washing, ball milling, slurrying and spray drying, obtain silica-gel carrier；
(b) the silica obtained carrier of step (a) is impregnated in the solution containing Pt component presoma and Zn component presoma
Then processing is successively removed solvent processing and drying,
Wherein, filtration washing described in step (a) carries out in purpose ceramic-film filter, in the material after filtration washing sodium ion with
The content of sodium element meter is not higher than 0.2 weight %.
2. according to the method described in claim 1, wherein, in step (a), the waterglass, inorganic acid solution, n-butanol and
The condition that glycerine is contacted includes: that temperature is 10-60 DEG C, time 1-5h, pH value 2-4.
3. according to the method described in claim 1, wherein, in step (a), the waterglass, inorganic acid solution, n-butanol and
The weight ratio of the dosage of glycerine is 3-6:1:0.8-2.5:0.8-2.5.
4. according to the method described in claim 1, wherein, in step (a), the inorganic acid solution is sulfuric acid, nitric acid and salt
At least one of acid aqueous solution.
5. according to the method described in claim 1, wherein, in step (b), the silica-gel carrier, Pt component presoma and Zn
The dosage of component presoma makes in the dehydrogenation of isobutane catalyst of preparation, and the total weight with the dehydrogenation of isobutane catalyst is
Benchmark, the content of the carrier are 98-99.4 weight %, and content of the Pt component in terms of Pt element is 0.1-0.5 weight %,
Content of the Zn component in terms of Zn element is 0.5-1.5 weight %.
6. the dehydrogenation of isobutane catalyst of the preparation of the method as described in any one of claim 1-5.
7. dehydrogenation of isobutane catalyst according to claim 6, wherein the dehydrogenation of isobutane catalyst include carrier with
And the Pt component and Zn component of load on the carrier, wherein the carrier is silica-gel carrier, and the silica-gel carrier is averaged
Particle diameter is 20-60 μm, specific surface area 300-600m2/ g, pore volume 0.1-2.5mL/g, pore-size distribution are bimodal point
Cloth, and the bimodal corresponding most probable pore size is respectively 1-4.5nm and 20-50nm.
8. dehydrogenation of isobutane catalyst according to claim 7, wherein with the total weight of the dehydrogenation of isobutane catalyst
On the basis of, the content of the carrier is 98-99.4 weight %, and content of the Pt component in terms of Pt element is 0.1-0.5 weight
% is measured, content of the Zn component in terms of Zn element is 0.5-1.5 weight %；
Preferably, the average grain diameter of the dehydrogenation of isobutane catalyst is 20-50 μm, specific surface area 320-420m2/ g,
Pore volume is 0.5-1.8mL/g, and pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 1.2-
4nm and 22-45nm.
9. a kind of method of preparing isobutene through dehydrogenation of iso-butane, which comprises in the presence of catalyst and hydrogen, by isobutyl
Alkane carries out dehydrogenation reaction, which is characterized in that the catalyst is that dehydrogenation of isobutane described in any one of claim 6-9 is urged
Agent.
10. according to the method described in claim 9, wherein, the molar ratio of the dosage of the dosage and hydrogen of iso-butane is 0.5-
1.5:1；
Preferably, it is 550-650 DEG C, reaction pressure 0.05-0.2MPa that the condition of the dehydrogenation reaction, which includes: reaction temperature,
Reaction time is 20-40h, and iso-butane mass space velocity is 2-5h-1。
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