CN110496630A - 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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- CN110496630A CN110496630A CN201810475361.XA CN201810475361A CN110496630A CN 110496630 A CN110496630 A CN 110496630A CN 201810475361 A CN201810475361 A CN 201810475361A CN 110496630 A CN110496630 A CN 110496630A
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- dehydrogenation
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- isobutane
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 273
- 239000001282 iso-butane Substances 0.000 title claims abstract description 137
- 235000013847 iso-butane Nutrition 0.000 title claims abstract description 137
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 126
- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 69
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000012065 filter cake Substances 0.000 claims abstract description 45
- 239000000969 carrier Substances 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000000741 silica gel Substances 0.000 claims abstract description 25
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 25
- 239000013335 mesoporous material Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 16
- 238000005470 impregnation Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000012545 processing Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000009826 distribution Methods 0.000 claims description 30
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- 230000002902 bimodal effect Effects 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 13
- 150000007522 mineralic acids Chemical class 0.000 claims description 12
- 235000019353 potassium silicate Nutrition 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- -1 polyoxyethylene Polymers 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000428 triblock copolymer Polymers 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 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
- 239000001273 butane Substances 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 24
- 239000000126 substance Substances 0.000 description 14
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 10
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 10
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 101150116295 CAT2 gene Proteins 0.000 description 6
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 6
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004231 fluid catalytic cracking Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- FAXVXGOUWBCEFQ-UHFFFAOYSA-N [C].CC(C)=C Chemical compound [C].CC(C)=C FAXVXGOUWBCEFQ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000011161 development Methods 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
- 238000001914 filtration Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007430 reference method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 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
- 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
- 239000005977 Ethylene Substances 0.000 description 1
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- 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
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes 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
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 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
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion 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
- 230000001788 irregular Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000005259 measurement Methods 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
- 239000004005 microsphere Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000005507 spraying Methods 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
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—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
-
- B01J35/40—
-
- B01J35/51—
-
- 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
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- 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
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) prepares meso-porous molecular sieve material；(b) silica gel is prepared；(c) the mesoporous material filter cake and silica gel filter cake are mixed into simultaneously ball milling, and will be spray-dried after the solid powder obtained after ball milling water slurrying, then by the template removal in obtained product, obtain spherical double mesoporous composite material carriers；(d) spherical double mesoporous composite material carriers obtained by step (c) are subjected to impregnation in the solution containing Pt component presoma and Zn component presoma, are then successively removed solvent processing, dry and roasting.Gained dehydrogenation of isobutane catalyst has preferable dehydrogenation activity and anti-carbon.
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
Glue, methyl ethyl ketone, polyisobutene, methyl methacrylate, isoprene, tertiary butyl phenol, tert-butylamine, 1,4- butanediol and ABS resin
Etc. various Organic Ingredients and fine chemicals.The main source of isobutene is the by-product of naphtha vapor cracking ethylene preparation device
By-product in C 4 fraction, the by-product C 4 fraction of refinery's fluid catalytic cracking (FCC) device and the synthesis of Halcon method propylene oxide
The tert-butyl alcohol (TAB).
In recent years, as the development and utilization of isobutene downstream product, the demand of isobutene increase year by year, traditional is different
Butylene production has been unable to meet chemical industry to the great demand of isobutene, therefore the research and development of isobutene production new technology
Work becomes a big hot spot of chemical industry.Wherein, most competitive technology has dehydrogenation of isobutane, n-butene skeletal isomerization
Change and novel FCC apparatus increases production isobutene.In these methods, the repercussion study of iso-butane direct dehydrogenation preparing isobutene is more early,
Through realizing industrialized production.There is C4 resource abundant in China, but the chemical utilization rate of China's C 4 fraction is lower, most of
Iso-butane is directly used as fuel, and waste is serious.It is rationally petrochemical industry research field face one urgent using C4 resource
Task.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, with it
Its metal oxide catalyst is compared, and noble metal catalyst activity is higher, and selectivity is preferable, and to more environment-friendly.But
It is to lead to catalyst higher cost since noble metal is expensive, and satisfaction also has not been reached yet in the performance of such catalyst
Degree.
In order to improve the reactivity worth of catalyst for preparing isobutene through dehydrogenation of iso-butane, researcher has done many work.Than
Such as: the preparation method by changing catalyst improves catalyst performance (Industrial Catalysis, 2014,22 (2): 148-153), passes through
It adds auxiliary agent and improves catalyst stability (Catal.Today, 2000,55 (3): 213-223), mentioned by improving carrier property
High catalyst carbon accumulation resisting ability (chemistry of fuel journal, 2013,41 (12): 1481-1487).However, currently used carrier ratio
Surface area is smaller, has both been unfavorable for active metal component in the dispersion of carrier surface, is also unfavorable for raw material and product in reaction process
Diffusion.
Therefore, how to improve the reactivity worth of dehydrogenation of isobutane catalyst is one, preparing isobutene through dehydrogenation of iso-butane field
Urgent problem to be solved.
Summary of the invention
The purpose of the invention is to overcome existing dehydrogenation of isobutane catalyst noble metal active component dispersion uneven
Even, catalytic activity and the poor defect of stability provide a kind of method for preparing dehydrogenation of isobutane catalyst and by party's legal system
The method of standby dehydrogenation of isobutane catalyst and preparing isobutene through dehydrogenation of iso-butane, method provided by the present invention is easily operated,
It is environmental-friendly and low in cost, and dehydrogenation of isobutane catalyst obtained by this method, in the very low situation of noble-metal-supported amount
Under, 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) in the presence of template, butanol, ethyl orthosilicate is contacted with sour agent, and will be obtained after contact
Product crystallization simultaneously filters, and obtains mesoporous material filter cake；
(b) waterglass is contacted with inorganic acid, and the product obtained after contact is filtered, obtain silica gel filter cake；
(c) the mesoporous material filter cake and silica gel filter cake are mixed into simultaneously ball milling, and the solid powder obtained after ball milling is used
It is spray-dried after water slurrying, then by the template removal in obtained product, obtains spherical double mesoporous composite materials
Carrier；
(d) spherical double mesoporous composite material carriers obtained by step (c) are being contained into Pt component presoma and Zn component forerunner
Impregnation is carried out in the solution of body, is then successively removed solvent processing, dry and roasting.
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 the iso-butane prepared by preceding method
Dehydrogenation.
Carrier structure (including the physical structures such as specific surface area, Kong Rong, pore-size distribution and the surface acid of noble metal catalyst
The chemical structures such as property position, Electronic Performance) not only the dispersion degree of active metal component is had a major impact, but also directly affect
Mass transfer and diffusion in reaction process.Therefore, the catalytic performances such as activity, selectivity and stability of heterogeneous catalyst both depended on
In the catalytic characteristics of active component, but it is related with the feature of catalyst carrier.In order to which the noble metal reduced in catalyst as far as possible contains
Amount, while the activity and stability of catalyst are improved, the preparation process of carrier is most important.Most of commercially active oxidation
Aluminium surface hydroxyl is excessive, acid too strong.The use of this kind of aluminium oxide is that carrier prepares dehydrogenation, is catalyzed during the reaction
Agent surface is easy to carbon distribution, and then leads to fast deactivation.
The present inventor passes through the study found that in the preparation process of dehydrogenation of isobutane catalyst, is had using containing
The composite material of the meso-porous molecular sieve material and silica that have three-dimensional cubic duct distributed architecture will have three as carrier
The pattern for tieing up the mesopore molecular sieve of cube pore distribution structure, the regular mesoporous spatial character of silica gel and spherical shape is excellent
Point combines, and can not only retain the high-specific surface area of ordered mesoporous material, the characteristics of macropore holds, also add aperture it is big and
The advantage of narrowly distributing, and unique bimodal distribution is presented in its pore-size distribution, dexterously has micro-sphere structure with aperture bimodal
The advantages of ordered mesoporous material of distribution, combines, more conducively the load of active component.
Compared with prior art, the dehydrogenation of isobutane catalyst of method preparation provided by the present invention has the advantage that
(1) the method preparation process provided by the present invention for preparing dehydrogenation of isobutane catalyst is simple, and condition is easy to control
System, good repetitiveness；
(2) 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, it can
The preparation cost of dehydrogenation of isobutane catalyst is effectively reduced；
(3) the dehydrogenation of isobutane catalyst of method preparation provided by the present invention, due to being loaded using the method for co-impregnation
The center Zn of active Pt component and Zn component, resulting structures oxidation is very high in high temperature reducing conditions stability inferior, can inhibit to carry
Body loads the inactivation of single Pt component, reduces carbon distribution, and effectively neutralizes the strong acid center of carrier surface, make carrier surface without
Acidity, and by the dispersion degree of geometric effect raising Pt component, so as to significantly reduce iso-butane anaerobic dehydrogenation preparing isobutene
Carbon distribution risk, the selectivity of raising purpose product and the stability of dehydrogenation of isobutane catalyst in reaction process；
(4) on the dehydrogenation of isobutane catalyst of method provided by the present invention preparation noble metal active component dispersion degree
It is higher, and then guarantee that iso-butane catalyst is not easy to inactivate because active metal particles are reunited during the reaction；
(5) the dehydrogenation of isobutane catalyst of method preparation provided by the present invention is used for iso-butane anaerobic dehydrogenation isobutyl
Good catalytic performance is shown when alkene reaction, iso-butane high conversion rate, selective isobutene is high, and catalyst stability is good,
Carbon deposition quantity is low.
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
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the X-ray diffraction spectrogram of the double mesoporous composite material carriers of spherical shape of embodiment 1；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the double mesoporous composite material carriers of spherical shape of embodiment 1；
Fig. 3 is the aperture structure distribution map of the double mesoporous composite material carriers of spherical shape 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, these ranges herein
Or value should be understood as comprising the value close to these ranges or value.For numberical range, the endpoint value of each range it
Between, can be combined with each other between the endpoint value and individual point value of each range, and individually between point value and obtain one
Or multiple new numberical ranges, 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) in the presence of template, butanol, ethyl orthosilicate is contacted with sour agent, and will be obtained after contact
Product crystallization simultaneously filters, and obtains mesoporous material filter cake；
(b) waterglass is contacted with inorganic acid, and the product obtained after contact is filtered, obtain silica gel filter cake；
(c) the mesoporous material filter cake and silica gel filter cake are mixed into simultaneously ball milling, and the solid powder obtained after ball milling is used
It is spray-dried after water slurrying, then by the template removal in obtained product, obtains spherical double mesoporous composite materials
Carrier；
(d) spherical double mesoporous composite material carriers obtained by step (c) are being contained into Pt component presoma and Zn component forerunner
Impregnation is carried out in the solution of body, is then successively removed solvent processing, dry and roasting.
In the forming process of above-mentioned dehydrogenation of isobutane catalyst, the mesoporous material filter cake is with three-dimensional cubic pore
The meso-porous molecular sieve material of road distributed architecture.
In the forming process of above-mentioned spherical double mesoporous composite material carriers, it is main by control mesoporous material filter cake and
The composition of silica gel filter cake controls pore-size distribution for bimodal distribution, and the double mesoporous composite material carriers of the spherical shape is made to have diplopore
Distributed architecture, and (that is, mesoporous material filter cake and silica gel filter cake are first mixed simultaneously ball milling, then will by control forming method
It is spray-dried after the water slurrying of obtained solid powder) microscopic appearance of spherical double mesoporous composite material carriers is controlled
For spherical shape, the common raw material being easy to get can be used, synthesizes under easy operating condition and has both the distribution of three-dimensional cubic duct
The double composite mesoporous materials of the spherical shape of the advantages of meso-porous molecular sieve material of structure, silica gel bring silica and ball type carrier
Expect that carrier, the carrier not only have porous structure, large specific surface area, the pore volume of meso-porous molecular sieve material larger and special
Microcellular structure and the characteristics of stronger adsorption capacity, also have the characteristics that good fluidity, and pass through impregnation supporting Pt
Component and Zn component, can be prepared by that surface is no acidic, dehydrogenation activity is good, selectivity is high, stability is strong and that anti-carbon is good is different
Butane dehydrogenation catalyst.
According to the present invention, during preparing mesoporous material filter cake, the dosage of each substance can be in a wider scope
It is selected and is adjusted.For example, the molar ratio of the template, butanol and ethyl orthosilicate can be 1 in step (a):
10-100:10-90, preferably 1:60-90:50-75.
According to the present invention, described in order to enable the mesoporous material filter cake arrived has three-dimensional cubic duct distributed architecture
The type of template is preferably triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene.Wherein, which can lead to
It crosses and is commercially available (for example, can be purchased from Aldrich, trade name P123, molecular formula EO20PO70EO20), it can also be with
It is prepared by existing various methods.When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the mould
The molal quantity of plate agent calculates to obtain according to the average molecular weight of polyoxyethylene-poly-oxypropylene polyoxyethylene.
According to the present invention, the sour agent can be used for adjusting for various routines pH value substance or mixture it is (such as molten
Liquid).The acid agent preferably uses in form of an aqueous solutions.Under preferable case, the acid agent is hydrochloric acid solution, the acid agent
PH value is 1-6.
According to the present invention, the butanol is preferably n-butanol.
According to the present invention, it is 10-60 DEG C that the condition that the ethyl orthosilicate is contacted with sour agent, which may include: temperature, the time
It is 10-72 hours, pH value 1-7；Under preferable case, the condition that the ethyl orthosilicate is contacted with sour agent may include: temperature
It is 10-30 DEG C, the time is 20-40 hours, pH value 3-6.In order to be more advantageous to the uniform mixing between each substance, the positive silicon
Acetoacetic ester is contacted with sour agent and is preferably carried out under agitation.It is described acid agent dosage preferably so that the ethyl orthosilicate with
The pH value of sour agent haptoreaction system is 1-7, more preferably 3-6.
It is 30-150 DEG C that the present invention, which may include: temperature to the condition of the crystallization, and the time is 10-72 hours, preferably feelings
Under condition, the condition of the crystallization includes: that temperature is 40-80 DEG C, and the time is 20-40 hours.The crystallization passes through hydrothermal crystallization method
Implement.
In addition, the present invention is not special to the way of contact between the template, butanol, sour agent and ethyl orthosilicate
Ground limits, for example, above-mentioned four kinds of substances can be mixed simultaneously, several substances therein can also be first mixed,
It will continue to be mixed in mixture that remaining substance is added again.Under preferable case, the way of contact is first to exist
At 10-100 DEG C, after template, butanol and sour agent are stirred, then add ethyl orthosilicate and continue to be stirred.
The method for preparing dehydrogenation of isobutane catalyst provided according to the present invention, in step (b), the waterglass with
The condition of inorganic acid contact may include: that temperature can be 10-60 DEG C, preferably 20-40 DEG C；Time can be 1-5 hours,
Preferably 1.5-3 hours, pH value 2-4.In order to be more advantageous to the uniform mixing between each substance, the waterglass and inorganic acid
Contact preferably carries out under agitation.
According to the present invention, the waterglass is the aqueous solution of the sodium metasilicate of this field routine, and concentration can be 10-50
Weight %, preferably 12-30 weight %.
According to the present invention, the inorganic acid can be one of sulfuric acid, nitric acid and hydrochloric acid or a variety of.The inorganic acid
It can use, can also be used in the form of its aqueous solution in pure form.The dosage of the inorganic acid is preferably so that water glass
The pH value of the contact conditions reaction system of glass and inorganic acid is 2-4.Preferably, the weight of the dosage of the waterglass and inorganic acid
Amount is than being 3-6:1.
In addition, it is above-mentioned prepare mesoporous material filter cake and silica gel filter cake during, the mistake of filter cake is obtained by filtering
Journey may include: after filtration, washs (washing times can be 2-10) repeatedly with distilled water, is then filtered.It is preferred that
Ground prepares the washing during mesoporous material filter cake so that filter cake pH is 7, and preparing the washing during silica gel filter cake makes
It obtains sodium ions content and is lower than 0.02 weight %.
According to the present invention, in step (c), the dosage of the mesoporous material filter cake and silica gel filter cake can be according to expection
The component of the double mesoporous composite material carriers of obtained spherical shape is selected, under preferable case, with the described mesoporous of 100 parts by weight
On the basis of the dosage of material filter cake, the dosage of the silica gel filter cake can be 1-200 parts by weight, preferably 50-150 parts by weight.
According to the present invention, the concrete operation method of the ball milling and condition be not to destroy or not destroy mesoporous material substantially
Structure and enter silica gel subject to mesoporous material duct.Those skilled in the art can select various conjunctions according to mentioned above principle
Suitable condition implements the present invention.Specifically, the ball milling carries out in the ball mill, wherein the diameter of abrading-ball can in ball mill
Think 2-3mm；The quantity of abrading-ball can reasonably be selected according to the size of ball grinder, be 50-150mL's for size
1 abrading-ball usually can be used in ball grinder；The material of the abrading-ball can be agate, polytetrafluoroethylene (PTFE) etc., preferably agate.
The condition of the ball milling includes: that the revolving speed of abrading-ball can be 300-500r/min, and the temperature in ball grinder can be 15-100
DEG C, the time of ball milling can be 0.1-100 hours.
In the present invention, the concrete operation method and condition of the spray drying are preferred are as follows: will be by the solid powder and water
The slurry being made into is added to high speed rotation in atomizer and is spray-dried with realizing.Wherein, the condition of the spray drying can wrap
Include: temperature can be 100-300 DEG C, and the revolving speed of rotation can be 10000-15000r/min；It is described spraying under preferable case
Dry condition includes: that temperature is 150-250 DEG C, and the revolving speed of rotation is 11000-13000r/min；Under most preferred case, institute
It is 200 DEG C that the condition for stating spray drying, which includes: temperature, and the revolving speed of rotation is 12000r/min.
According to the present invention, the method for removed template method is preferably calcination method.The condition of the removed template method can wrap
Include: temperature is 300-600 DEG C, preferably 350-550 DEG C, most preferably 500 DEG C；Time is 10-80 hours, preferably 20-30
Hour, most preferably 24 hours.
According to the present invention, in step (d), spherical double mesoporous composite material carrier to load metal components can be adopted
With the mode of dipping, enter metal component by the capillary pressure of the cellular structure of the carrier described spherical double mesoporous multiple
In the duct of condensation material carrier, while metal component can also be in the adsorption of spherical double mesoporous composite material carriers, directly
Reach adsorption equilibrium on the surface of the carrier to metal component.The impregnation can be handled for co-impregnation, or
Step impregnation processing.In order to save preparation cost, simplify experimental technique, the impregnation is preferably co-impregnation processing；Into one
Preferably, the condition of the co-impregnation processing includes: that spherical double mesoporous composite material carriers are being contained Pt component forerunner to step
The solution of body and Zn component presoma is mixed, and the temperature of the dipping can be 25-50 DEG C, the dipping when
Between can be 2-6h.
According to the present invention, the Pt component presoma is preferably H2PtCl6, the Zn component presoma is preferably Zn
(NO3)2。
The present invention does not limit the concentration of the solution containing Pt component presoma and Zn component presoma particularly
It is fixed, 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,
The concentration of the Zn component presoma can be 0.015-0.1mol/L.
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 (d), the drying can carry out in drying box, and the roasting can be in Muffle
It is carried out in furnace.The condition of the drying may include: that temperature is 110-150 DEG C, time 3-6h；The condition of the roasting can
To include: temperature for 600-650 DEG C, time 5-8h.
According to the present invention, in step (d), spherical double mesoporous composite material carriers, Pt component presoma and Zn group
The dosage of presoma is divided to make in the dehydrogenation of isobutane catalyst of preparation, 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
% is measured, content of the Zn component in terms of Zn element is 0.5-1.5 weight %.
Under preferable case, the use of spherical double mesoporous composite material carriers, Pt component presoma and Zn component presoma
Amount so that preparation dehydrogenation of isobutane catalyst in, on the basis of the total weight of the dehydrogenation of isobutane catalyst, the carrier
Content be 98.4-99 weight %, content of the Pt component in terms of Pt element be 0.2-0.4 weight %, the Zn component with
The content of Zn element meter is 0.8-1.2 weight %.
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 includes the Pt component of carrier and load on the carrier
With Zn component, wherein the carrier is spherical double mesoporous composite material carriers, and spherical double mesoporous composite material carriers contain
There are meso-porous molecular sieve material and silica with three-dimensional cubic duct distributed architecture, spherical double mesoporous composite materials
The average grain diameter of carrier is 30-60 μm, specific surface area 150-600m2/ g, pore volume 0.5-2mL/g, pore-size distribution are double
Peak distribution, and the bimodal corresponding most probable pore size is respectively 4-8nm and 20-30nm.
According to the present invention, in the dehydrogenation of isobutane catalyst, it is special that spherical double mesoporous composite material carriers have
Three-dimensional cubic road distributed architecture, the average grain diameter of particle measured using laser fineness gage, specific surface area, pore volume
It is measured with most probable pore size according to nitrogen adsorption methods.In the present invention, granularity refers to the particle size of feed particles, works as raw material
The diameter of then granularity sphere indicates when particle is sphere, the then side length of granularity cube when feed particles are cube
It indicates, when feed particles are irregular shape, then granularity uses just the mesh that can screen out the sieve of the feed particles
Size Expressing.
According to the present invention, the spherical double mesoporous composite material carriers are by by spherical double mesoporous composite material carriers
Particle size controls within above range, it can be ensured that and spherical double mesoporous composite material carriers are not susceptible to reunite, and
And it is former to be used as the reaction that loaded catalyst made of carrier can be improved in preparing isobutene through dehydrogenation of iso-butane reaction process
Expect conversion ratio.When the specific surface area of spherical double mesoporous composite material carriers is less than 150m2/ g and/or pore volume are less than
When 0.5mL/g, the catalytic activity for being used as loaded catalyst made of carrier can be significantly reduced；As spherical double Jie
The specific surface area of hole composite material carrier is greater than 600m2When/g and/or pore volume are greater than 2mL/g, it is used as made of carrier
Loaded catalyst is easy to happen reunion in preparing isobutene through dehydrogenation of iso-butane reaction process, thus the dehydrogenation of isobutane system of influence
Reaction raw materials conversion ratio during isobutene reaction.
In the preferred case, the average grain diameter of spherical double mesoporous composite material carriers is 20-55 μm, specific surface area
For 180-600m2/ g, pore volume 0.8-1.4mL/g, pore-size distribution are bimodal distribution, and the bimodal corresponding most probable
Aperture is respectively 4.5-7.5nm and 21-29nm.
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 %, and the Zn component is in terms of Zn element
Content 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 %, and the Zn component is in terms of Zn element
Content be 0.8-1.2 weight %.
In the present invention, the content of each element can use x-ray fluorescence light in the dehydrogenation of isobutane catalytic component
Spectrum analysis method measures.
It is further preferred that the average particle diameter of the dehydrogenation of isobutane catalyst is 30-60 μm, specific surface area is
100-500m2/ g, pore volume 0.4-1.8mL/g, pore-size distribution are bimodal distribution, and the bimodal corresponding most probable hole
Diameter is respectively 4-8nm and 20-30nm.
According to the present invention, in spherical double mesoporous composite material carriers, to have three-dimensional described in 100 parts by weight
On the basis of the weight of the meso-porous molecular sieve material of cube pore distribution structure, the weight of the silica is 1-200 weight
Part, preferably 50-150 parts by weight.
According to the present invention, the silica that spherical double mesoporous composite material carriers contain is introduced by silica gel.It is " logical
Cross the silica that silica gel is introduced into " refer in the preparation process of spherical double mesoporous composite material carriers, by silica gel conduct
Prepare the silica component that raw material is brought into the double mesoporous composite material carriers of the spherical shape finally prepared.In spherical double Jie
In hole composite material carrier, relative to the mesopore molecular sieve material described in 100 parts by weight with three-dimensional cubic duct distributed architecture
The weight of material, the content of the silica introduced by silica gel can be 1-200 parts by weight, preferably 50-150 weight
Part.
According to the present invention, the meso-porous molecular sieve material with three-dimensional cubic duct distributed architecture can be this field
Conventional use of meso-porous molecular sieve material, and 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.
The dehydrogenation of isobutane catalyst of method preparation provided by the present invention is used for catalyzing iso-butane alkane dehydrogenation preparing isobutene
When, 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, isobutyl
The molar ratio of the dosage of the dosage and hydrogen of alkane is 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, example
Such as, it is 550-650 DEG C, reaction pressure 0.05-0.2MPa that the condition of the dehydrogenation reaction, which may include: reaction temperature, reaction
Time is 20-40h, and iso-butane mass space velocity is 2-5h-1。
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from
Aldrich is abbreviated as P123, molecular formula EO20PO70EO20, it is 9003-11-6 in the registration number of U.S. chemical abstract
Substance, average molecular mass Mn 5800.
In following embodiment and comparative example, X-ray diffraction analysis is in the model for being purchased from Bruker AXS company, Germany
It is carried out on the X-ray diffractometer of D8Advance；Scanning electron microscope analysis is swept the model XL-30's purchased from U.S. FEI company
It retouches and is carried out on electron microscope；Pore structure parameter analysis is in the ASAP2020-M purchased from the production of U.S. Micromeritics company
It is carried out on+c-type adsorption instrument, the specific surface area and pore volume of sample, which calculate, uses BET method；The particle diameter distribution of sample is in Ma Er
It is carried out on literary laser particle analyzer；Rotary Evaporators are the production of IKA company, Germany, model RV10digital；Dehydrogenation of isobutane
The activity component load quantity of catalyst is penetrated in the wavelength dispersion X for being Axios-Advanced purchased from Dutch Panaco company model
It is measured in line Fluorescence Spectrometer；The analysis of reaction product ingredient is in the gas chromatograph for being purchased from agilent company model 7890A
Upper progress.
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 spherical double mesoporous composite material carriers
It is water-soluble for 4 hydrochloric acid that 6g (0.001mol) triblock copolymer surfactant P123 is dissolved in 10ml, pH value
In liquid and 220ml deionized water solution, stirring 4h to P123 dissolution forms clear solution, then be added into the clear solution
6g (0.08mol) n-butanol simultaneously stirs 1h, is subsequently placed in 40 DEG C of water-bath, and 12.9g (0.062mol) ethyl orthosilicate is slow
Slowly be added drop-wise in the solution, keep the temperature at about 40 DEG C, pH value be 4.5 under conditions of stir for 24 hours, then again at 100 DEG C
Hydro-thermal process for 24 hours, be then filtered and and be washed with deionized 4 times, then filter and obtain with three-dimensional cubic duct
Meso-porous molecular sieve material filter cake A1.
It is the sulfuric acid solution of 12 weight % with weight ratio by waterglass and concentration that concentration is 15 weight % is that 5:1 is carried out
It mixes and the haptoreaction 2h at 30 DEG C, then adjusts pH value to 3 with the sulfuric acid that concentration is 98 weight %, then to obtaining
Reaction mass is filtered, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel filter cake B1.
The 10g filter cake A1 and 10g filter cake B1 of above-mentioned preparation is put into togerther in 100ml ball grinder, wherein ball grinder
Material is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 400r/min.Envelope
Ball grinder is closed, temperature is to obtain 30g solid powder ball milling 1 hour at 60 DEG C in ball grinder；The solid powder is dissolved in
In 30 grams of deionized waters, it is spray-dried at 200 DEG C in the case where revolving speed is 12000r/min；The product that will be obtained after spray drying
It is calcined 24 hours at 500 DEG C in Muffle furnace, removed template method, obtains 30g with three-dimensional cubic duct distributed architecture
Spherical double mesoporous composite material support Cs 1.
(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 obtained
It is molten to be immersed in the mixture by mixture solution for the spherical double mesoporous composite material support Cs 1 of 10g that step (1) is prepared
In liquid, after impregnating 5h at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product, by solid product
It is placed in the drying box that temperature is 120 DEG C, dry 3h.Then in Muffle furnace, temperature is 600 DEG C of roasting 6h, obtains iso-butane
Dehydrogenation Cat-1 (on the basis of the total weight of dehydrogenation of isobutane catalyst Cat-1, content of the Pt component in terms of Pt element
It is 1 weight % for content of 0.3 weight %, the Zn component in terms of Zn element, remaining is carrier).
With XRD, scanning electron microscope and ASAP2020-M+C type adsorption instrument come to spherical double mesoporous composite material carriers
C1 and dehydrogenation of isobutane catalyst Cat-1 are characterized.
Fig. 1 is X-ray diffracting spectrum, wherein curve is the XRD spectrum of spherical double mesoporous composite material support Cs 1 in figure
Figure, abscissa are 2 θ, and ordinate is intensity, and the low-angle spectral peak occurred by XRD spectra is it is found that spherical double mesoporous composite materials
The XRD spectra of support C 1 has the hexagonal hole road structure of 2D specific to mesoporous material；
Fig. 2 is SEM scanning electron microscope (SEM) photograph, and as seen from the figure, the microscopic appearance of spherical double mesoporous composite material support Cs 1 is particle
The Mesoporous Spheres that degree is 30-60 μm；
Fig. 3 is pore size distribution curve figure, it can be seen from the figure that the hole of spherical double mesoporous composite material support Cs 1
Diameter is distributed as bimodal distribution, and duct is highly uniform.
Table 1 is the pore structure parameter of spherical double mesoporous composite material support Cs 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) |
| Support C 1 | 271 | 1.7 | 7.2,25 | 30-60 |
| Catalyst Cat-1 | 243 | 1.5 | 7,23.3 | 30-60 |
*: 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.
Spherical double mesoporous composite material carriers are after supporting Pt component and Zn component it can be seen from the data of table 1,
Specific surface area and pore volume are reduced, and for this explanation during load-reaction, Pt component and Zn component enter spherical pair
The inside of mesoporous composite material carrier.
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, it is de- preparing iso-butane
During hydrogen catalyst, spherical double mesoporous composite material carriers are replaced with the alumina support of identical weight, thus point
It Zhi get not 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, it is de- preparing iso-butane
The step of not being spray-dried during hydrogen catalyst, and be only supported on Pt component and Zn component by the method impregnated
On carrier, so that carrier D2 and dehydrogenation of isobutane catalyst Cat-D-2 be made respectively.
Comparative example 3
Carrier and dehydrogenation of isobutane catalyst are prepared according to the method for embodiment 1, the difference is that preparing iso-butane
In the dipping process of de- hydrogen type catalyst, Zn (NO is not added3)2·6H20.080g H is only added in O2PtCl6·6H2O, by altogether
Single Pt component is only supported on spherical double mesoporous composite material carriers by infusion process, so that dehydrogenation of isobutane catalyst be made
Cat-D-3, on the basis of the total weight of dehydrogenation of isobutane catalyst Cat-D-3, 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 spherical double mesoporous composite material carriers
It is water-soluble for 4 hydrochloric acid that 6g (0.001mol) triblock copolymer surfactant P123 is dissolved in 10ml, pH value
In liquid and 220ml deionized water solution, stirring 4h to P123 dissolution forms clear solution, then be added into the clear solution
6.7g (0.09mol) n-butanol simultaneously stirs 1h, is subsequently placed in 40 DEG C of water-bath, by 10.4g (0.05mol) ethyl orthosilicate
Be slowly dropped in the solution, keep the temperature at about 40 DEG C, pH value be 5 under conditions of stir for 24 hours, then again at 90 DEG C
Hydro-thermal process 36h, be then filtered and and be washed with deionized 4 times, then filter and obtain with three-dimensional cubic duct
Meso-porous molecular sieve material filter cake A2；
It is the sulfuric acid solution of 12 weight % with weight ratio by waterglass and concentration that concentration is 15 weight % is that 4:1 is carried out
It mixes and the haptoreaction 1.5h at 40 DEG C, then adjusts pH value to 2 with the sulfuric acid that concentration is 98 weight %, then to obtaining
Reaction mass filtered, and be washed with distilled water to sodium ions content be 0.02 weight %, obtain silica gel filter cake B2.
The 20g filter cake A2 and 10g filter cake B2 of above-mentioned preparation is put into togerther in 100ml ball grinder, wherein ball grinder
Material is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 300r/min.Envelope
Ball grinder is closed, temperature is to obtain 38g solid powder ball milling 0.5 hour at 80 DEG C in ball grinder；The solid powder is dissolved
In 12g deionized water, it is spray-dried at 250 DEG C in the case where revolving speed is 11000r/min；The product that will be obtained after spray drying
It is calcined 15 hours at 500 DEG C in Muffle furnace, removed template method, obtains 35g with three-dimensional cubic duct pore distribution knot
The double mesoporous composite material support Cs 2 of the spherical shape of structure.
(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 obtained
It is molten to be immersed in the mixture by mixture solution for the spherical double mesoporous composite material support Cs 2 of 10g that step (1) is prepared
In liquid, after impregnating 5h at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product, by solid product
It is placed in the drying box that temperature is 120 DEG C, dry 3h.Then in Muffle furnace, temperature is 600 DEG C of roasting 6h, obtains iso-butane
Dehydrogenation Cat-2 (on the basis of the total weight of dehydrogenation of isobutane catalyst Cat-2, content of the Pt component in terms of Pt element
It is 1 weight % for content of 0.3 weight %, the Zn component in terms of Zn element, remaining is carrier).
Table 2 is the pore structure parameter of spherical double mesoporous composite material support Cs 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) |
| Support C 2 | 260 | 1.5 | 7.5,24 | 35-55 |
| Catalyst Cat-2 | 235 | 1.4 | 7.4,22.9 | 35-55 |
*: 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.
Spherical double mesoporous composite material carriers are after supporting Pt component and Zn component it can be seen from the data of table 2,
Specific surface area and pore volume are reduced, and for this explanation during load-reaction, Pt component and Zn component enter spherical pair
The inside of mesoporous composite material carrier.
Embodiment 3
The present embodiment is for illustrating dehydrogenation of isobutane catalyst and preparation method thereof.
(1) preparation of spherical double mesoporous composite material carriers
It is water-soluble for 4 hydrochloric acid that 6g (0.001mol) triblock copolymer surfactant P123 is dissolved in 10ml, pH value
In liquid and 220ml deionized water solution, stirring 4h to P123 dissolution forms clear solution, then be added into the clear solution
5.2g (0.07mol) n-butanol simultaneously stirs 1h, is subsequently placed in 40 DEG C of water-bath, by 12.5g (0.06mol) ethyl orthosilicate
Be slowly dropped in the solution, keep the temperature at about 40 DEG C, pH value be 5 under conditions of stir for 24 hours, then again at 100 DEG C
Hydro-thermal process 36h, be then filtered and and be washed with deionized 4 times, then filter and obtain with three-dimensional cubic duct
Meso-porous molecular sieve material filter cake A3；
It is the sulfuric acid solution of 12 weight % with weight ratio by waterglass and concentration that concentration is 15 weight % is that 6:1 is carried out
It mixes and the haptoreaction 3h at 20 DEG C, then adjusts pH value to 4 with the sulfuric acid that concentration is 98 weight %, then to obtaining
Reaction mass is filtered, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel filter cake B3.
The 20g filter cake A3 and 30g filter cake B3 of above-mentioned preparation is put into togerther in 100ml ball grinder, wherein ball grinder
Material is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 550r/min.Envelope
Ball grinder is closed, temperature is to obtain 55g solid powder ball milling 10 hours at 40 DEG C in ball grinder；The solid powder is dissolved in
In 30g deionized water, it is spray-dried at 150 DEG C in the case where revolving speed is 13000r/min；The product obtained after spray drying is existed
It is calcined 70 hours at 450 DEG C in Muffle furnace, removed template method, obtains the ball that 53g has three-dimensional cubic duct distributed architecture
The double mesoporous composite material support Cs 3 of shape.
(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 obtained
It is molten to be immersed in the mixture by mixture solution for the spherical double mesoporous composite material support Cs 3 of 10g that step (1) is prepared
In liquid, after impregnating 5h at 25 DEG C, the aqueous solvent in system is boiled off with Rotary Evaporators, obtains solid product, by solid product
It is placed in the drying box that temperature is 120 DEG C, dry 3h.Then in Muffle furnace, temperature is 600 DEG C of roasting 6h, obtains iso-butane
Dehydrogenation Cat-3 (on the basis of the total weight of dehydrogenation of isobutane catalyst Cat-3, content of the Pt component in terms of Pt element
It is 1 weight % for content of 0.3 weight %, the Zn component in terms of Zn element, remaining is carrier).
Table 3 is the pore structure parameter of spherical double mesoporous composite material support Cs 3 and dehydrogenation of isobutane catalyst Cat-3.
Table 3
*: 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.
Spherical double mesoporous composite material carriers are after supporting Pt component and Zn component it can be seen from the data of table 3,
Specific surface area and pore volume are reduced, and for this explanation during load-reaction, Pt component and Zn component enter spherical pair
The inside of mesoporous composite material carrier.
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 equipped with hydrogen flame detector (FID)
Gas chromatograph carries out on-line analysis, obtains iso-butane conversion ratio and selective isobutene is as shown in table 4.Make after reaction
With the carbon distribution in the TGA/DSC1 thermogravimetric analyzer measurement dehydrogenation of isobutane catalyst Cat-1 of METTLER-TOLEDO company
Amount, 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, iso-butane is respectively adopted
Dehydrogenation Cat-2 and dehydrogenation of isobutane catalyst Cat-3 replaces dehydrogenation of isobutane catalyst Cat-1.Iso-butane conversion
The carbon deposition quantity of rate, selective isobutene and dehydrogenation of isobutane catalyst is as shown in table 4.
Experimental comparison's example 1-3
Preparing isobutene through dehydrogenation of iso-butane is carried out according to the method for EXPERIMENTAL EXAMPLE 1, unlike, iso-butane is respectively adopted
Dehydrogenation Cat-D-1~Cat-D-3 replaces dehydrogenation of isobutane catalyst Cat-1.Iso-butane conversion ratio, isobutene selection
The carbon deposition quantity of property and 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 | 24% | 92% | 1.3wt% |
| EXPERIMENTAL EXAMPLE 2 | Cat-2 | 23.5% | 91.8% | 1.2wt% |
| EXPERIMENTAL EXAMPLE 3 | Cat-3 | 23.4% | 91.5% | 1.4wt% |
| Experimental comparison's example 1 | Cat-D-1 | 12.1% | 71.3% | 5.3wt% |
| Experimental comparison's example 2 | Cat-D-2 | 18.7% | 85.2% | 2.2wt% |
| Experimental comparison's example 3 | Cat-D-3 | 6.5% | 56.3% | 6.8wt% |
From table 4, it can be seen that being catalyzed using the dehydrogenation of isobutane of the double mesoporous composite material carrier preparations of spherical shape of the invention
Agent for preparing isobutene through dehydrogenation of iso-butane react when, reaction 24 hours after, still available higher iso-butane conversion ratio and
Selective isobutene illustrates that dehydrogenation of isobutane catalyst of the invention not only has preferable catalytic performance, but also stability
Good, 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.Of the invention
, can be with various simple variants of the technical solution of the present invention are made in range of the technology design, including each technical characteristic is with any
Other suitable methods are combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, are belonged to
In protection scope of the present invention.
Claims (11)
1. a kind of method for preparing dehydrogenation of isobutane catalyst, which is characterized in that method includes the following steps:
(a) in the presence of template, butanol, product that ethyl orthosilicate is contacted with sour agent, and will obtained after contact
Crystallization simultaneously filters, and obtains mesoporous material filter cake；
(b) waterglass is contacted with inorganic acid, and the product obtained after contact is filtered, obtain silica gel filter cake；
(c) the mesoporous material filter cake and silica gel filter cake are mixed into simultaneously ball milling, and the solid powder water system that will be obtained after ball milling
It is spray-dried after slurry, then by the template removal in obtained product, obtains spherical double mesoporous composite material carriers；
(d) by spherical double mesoporous composite material carriers obtained by step (c) containing Pt component presoma and Zn component presoma
Impregnation is carried out in solution, is then successively removed solvent processing, dry and roasting.
2. according to the method described in claim 1, wherein, in step (a), the template, butanol and ethyl orthosilicate
Molar ratio is 1:10-100:10-90；
Preferably, the template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, and the acid agent is pH value
For the hydrochloric acid of 1-6, the butanol is n-butanol；
It is further preferred that it is 10-60 DEG C that the condition that ethyl orthosilicate is contacted with sour agent, which includes: temperature, the time is that 10-72 is small
When, pH value 1-7；The condition of the crystallization includes: that temperature is 30-150 DEG C, and the time is 10-72 hours.
3. according to the method described in claim 1, wherein, in step (b), condition packet that the waterglass is contacted with inorganic acid
Include: temperature is 10-60 DEG C, and the time is 1-5 hours, pH value 2-4；The inorganic acid is one of sulfuric acid, nitric acid and hydrochloric acid
Or it is a variety of.
4. according to the method described in claim 1, wherein, in step (c), with the mesoporous material filter cake of 100 parts by weight
Dosage on the basis of, the dosage of the silica gel filter cake is 1-200 parts by weight, preferably 50-150 parts by weight.
5. according to the method described in claim 1, wherein, in step (d), spherical double mesoporous composite material carriers, Pt
The dosage of component presoma and Zn component presoma to urge in the dehydrogenation of isobutane catalyst of preparation with the dehydrogenation of isobutane
On the basis of the total weight of agent, the content of spherical double mesoporous composite material carriers is 98-99.4 weight %, the Pt component
Content in terms of Pt element is 0.1-0.5 weight %, and 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 spherical double mesoporous composite material carriers, described
Spherical double mesoporous composite material carriers contain meso-porous molecular sieve material and silica with three-dimensional cubic duct distributed architecture,
The average grain diameter of spherical double mesoporous composite material carriers is 30-60 μm, specific surface area 150-600m2/ g, pore volume are
0.5-2mL/g, pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 4-8nm and 20-30nm.
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 particle diameter of the dehydrogenation of isobutane catalyst is 30-60 μm, specific surface area 100-500m2/ g,
Pore volume is 0.4-1.8mL/g, and pore-size distribution is bimodal distribution, and the bimodal corresponding most probable pore size is respectively 4-8nm
And 20-30nm.
9. dehydrogenation of isobutane catalyst according to claim 7, wherein to have three-dimensional cubic described in 100 parts by weight
On the basis of the weight of the meso-porous molecular sieve material of pore distribution structure, the weight of the silica is 1-200 parts by weight, preferably
For 50-150 parts by weight.
10. a kind of method of preparing isobutene through dehydrogenation of iso-butane, which comprises, will be different in the presence of catalyst and hydrogen
Butane carries out dehydrogenation reaction, which is characterized in that the catalyst is dehydrogenation of isobutane described in any one of claim 6-9
Catalyst.
11. according to the method described in claim 10, 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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