CN106140217A - A kind of halide preparing isobutene catalyst with anti-carbon performance and preparation method thereof - Google Patents
A kind of halide preparing isobutene catalyst with anti-carbon performance and preparation method thereof Download PDFInfo
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- CN106140217A CN106140217A CN201510135817.4A CN201510135817A CN106140217A CN 106140217 A CN106140217 A CN 106140217A CN 201510135817 A CN201510135817 A CN 201510135817A CN 106140217 A CN106140217 A CN 106140217A
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 150000004820 halides Chemical class 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 46
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011787 zinc oxide Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims abstract description 10
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- -1 zinc halide Chemical class 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000026030 halogenation Effects 0.000 claims abstract description 6
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 5
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910003452 thorium oxide Inorganic materials 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 59
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 45
- 239000007789 gas Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- 150000002367 halogens Chemical class 0.000 claims description 19
- 230000009467 reduction Effects 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052756 noble gas Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 239000008246 gaseous mixture Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229950005228 bromoform Drugs 0.000 claims description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 25
- 229910052593 corundum Inorganic materials 0.000 description 18
- 229910001845 yogo sapphire Inorganic materials 0.000 description 18
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 18
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 16
- 229910004369 ThO2 Inorganic materials 0.000 description 12
- 238000005070 sampling Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VGBPIHVLVSGJGR-UHFFFAOYSA-N thorium(4+);tetranitrate Chemical compound [Th+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VGBPIHVLVSGJGR-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229940102001 zinc bromide Drugs 0.000 description 3
- 239000004215 Carbon black (E152) Substances 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
- 238000011161 development Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910001509 metal bromide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920005479 Lucite® Polymers 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- XDYHDLLKHFVVSE-UHFFFAOYSA-N hydrate;dihydrobromide Chemical compound O.Br.Br XDYHDLLKHFVVSE-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of halide preparing isobutene catalyst with anti-carbon performance and preparation method thereof.In described catalyst, zinc oxide weight content is 0.5%-20%, and zinc halide weight content is 10%-50%, and thorium oxide weight content is 0.1%-20%, and surplus is alumina catalyst support.Catalyst preparation process is as follows: zinc precursor is dissolved in the water by (1), uses equi-volume impregnating to be carried on carrier, prepares catalyst precarsor after drying, roasting；(2) thorium presoma is dissolved in ethanol, uses equi-volume impregnating to be carried on catalyst precarsor prepared by step (1), after drying, roasting, prepare the catalyst precarsor that thorium is modified；(3) catalyst precarsor that step (2) gained thorium is modified is carried out halogenation treatment；Prepare halide preparing isobutene catalyst.This catalyst anti-carbon performance is strong, can prepare high selective isobutene. simultaneously.
Description
Technical field
The present invention relates to the preparation method of a kind of halide preparing isobutene catalyst, relate in particular to a kind of halide preparing isobutene catalyst with anti-carbon performance and preparation method thereof.
Background technology
Isobutene. is a kind of important basic organic chemical industry raw material, and derived product is numerous, and vertical industry chain is complicated, and consumption structure is diversified trend.Multiple high value-added product can be prepared for raw material, such as: multiple Organic Chemicals and the fine chemistry products such as butyl rubber, polyisobutylene, methyl tertiary butyl ether(MTBE), isoprene and lucite with isobutene..Owing to the market scale of isobutene. downstream product constantly expands, its imbalance between supply and demand will gradually highlight, and particularly under the background of petroleum resources exhaustion day by day, isobutene. yield has become the critical bottleneck of restriction downstream industry development.Therefore, the isobutene. syntheti c route of exploitation non-petroleum base, extremely the most urgent.
Methane is the main component of natural gas, the important research content during therefore methane trans-utilization just becomes gas chemical industry's technology.The most in recent years, develop fast development at shale gas, if it is possible to produce isobutene. from methane, an important approach will be provided for obtaining isobutene..But methane stable in properties, the most easily-activated, become the bottleneck of methane chemical utilization.Both at home and abroad many researcheres carry out methane activation, Study on Transformation one after another, among these, methane transformation technology again after halogen functional groupization, it is expected to become an important breakthrough mouth of a solution methane transformation technology difficult problem.
Bromomethane is important methane halides, can the many chemical products of preparation from bromomethane.Chinese patent CN 101041609A, CN 101284232A disclose one by methane at oxygen and HBr/H2Being converted into bromomethane under the effect of O, then bromomethane reacts the method generating C3 ~ C13 mixing high-carbon hydrocarbon further, and the hydrocarbon selective of more than C5 is 70%.Wherein, HBr for methane bromination, then discharges in first reactor in second reactor, recovered after be used further in back reaction, it is achieved the recycling of HBr.(CN 102527427A, the Jieli such as Wang Ye
He, Ting Xu, Zhihui Wang, et.al. Angew. Chem. Int. Ed. 2012,51,2438-2442) modified molecular sieve catalyst disclosing a kind of halide propylene and preparation method thereof.By using fluorochemical moditied processing molecular sieve, obtaining a kind of containing appropriate microporous structure and the catalyst of acidity, this catalyst can effectively be catalyzed halide and be converted into the reaction of propylene.Prepared catalyst one way bromomethane conversion ratio in the reaction that bromomethane is preparing propylene transformed is 35 ~ 99%, and the selectivity of propylene is 27 ~ 70%；In the reaction that chloromethanes is preparing propylene transformed, one way methyl chloride conversion rate is 30 ~ 99%, and the selectivity of propylene is 15 ~ 70%.Ivan M. Lorkovic et al. (Ivan M. Lorkovic, Aysen Yilmaz, Gurkan A. Yilmaz, et al.
Catalysis Today, 2004,98,317-322) it is also proposed that generate bromo-hydrocarbons with bromine with the alkane reaction in natural gas, then on metal oxide catalyst, bromo-hydrocarbons is converted into dimethyl ether, methanol and metal bromide, obtain metal-oxide after metal bromide oxygen recovery and discharge simple substance bromine, completing the circulation of bromine.
At present, it is mainly methanol and dimethyl ether about purpose product in the existing document that halide converts, additionally also have acetic acid, higher hydrocarbons, ethylene and propylene, and in the technology with alkene as target product, product mostly is ethylene, propylene, and single selectivity of product is the highest, and not yet find the relevant report of bromomethane high selectivity isobutene..
Summary of the invention
According to the deficiencies in the prior art, it is an object of the invention to provide a kind of halide preparing isobutene catalyst with anti-carbon performance and preparation method thereof.
A kind of halide preparing isobutene catalyst with anti-carbon performance, it is characterised in that: in described catalyst, zinc oxide weight content is 0.5%-20%, preferably 1%-15%, further preferred 1%-9%；Zinc halide weight content is 10%-50%, preferably 15%-45%, further preferred 18%-39%；Thorium oxide weight content is 0.1%-20%, preferably 0.1%-15%, more preferably 0.5%-5%, and surplus is alumina catalyst support.Described zinc halide includes one or more in zinc fluoride, zinc chloride, zinc bromide, zinc iodide, preferably zinc bromide.
Above-mentioned halide preparing isobutene catalyst, it is characterised in that: in described halide preparing isobutene catalyst, less than 450 DEG C total acid content (NH3-TPD) it is 0.5mmol/g-1.3mmol/g, preferably 0.6mmol/g-1.2mmol/g, more preferably 0.7mmol-1.1mmol/g；The acid content of 250 DEG C-350 DEG C accounts for the 20%-90% of less than 450 DEG C total acid contents, preferably 30%-80%, more preferably 40%-80%.
The present invention provides the preparation method of above-mentioned catalyst, and this preparation method comprises the steps:
(1) zinc precursor is dissolved in the water, uses equi-volume impregnating to be carried on carrier, after drying, roasting, prepare catalyst precarsor；
(2) thorium presoma is dissolved in the water, uses equi-volume impregnating to be carried on catalyst precarsor prepared by step (1), after drying, roasting, prepare the catalyst precarsor of additive modification；
(3) catalyst precarsor of step (2) gained additive modification is carried out halogenation treatment；Prepare halide preparing isobutene catalyst.
The inventive method, described in step (1), zinc precursor is inorganic salt or organic salt, preferably zinc nitrate, zinc chloride, zinc acetate, more preferably zinc nitrate.
The inventive method, described in step (1), baking temperature is 50 DEG C-200 DEG C, preferably 60 DEG C-150 DEG C, more preferably 80 DEG C-120 DEG C；Drying time is 1h-24h, preferably 4h-8h；Can be vacuum drying time dry, it is also possible to for being dried under the conditions of inert gas shielding, it is also possible to be dried in air atmosphere.Sintering temperature is 200 DEG C-800 DEG C, preferably 400 DEG C-600 DEG C；Roasting time is 1h-24h, preferably 4h-8h；It can be roasting under the conditions of inert gas shielding during roasting, it is also possible to roasting in air atmosphere.
The inventive method, described in step (2), thorium presoma is inorganic salt or organic salt, preferably nitrate, chlorate, acetate, more preferably nitrate.
The inventive method, described in step (2), baking temperature is 50 DEG C-200 DEG C, preferably 60 DEG C-150 DEG C, more preferably 80 DEG C-120 DEG C；Drying time is 1h-24h, preferably 4h-8h；Can be vacuum drying time dry, it is also possible to for being dried under the conditions of inert gas shielding, it is also possible to be dried in air atmosphere.Sintering temperature is 200 DEG C-800 DEG C, preferably 400 DEG C-600 DEG C；Roasting time is 1h-24h, preferably 4h-8h；It can be roasting under the conditions of inert gas shielding during roasting, it is also possible to roasting in air atmosphere.
The inventive method, described in step (3), halogenation treatment is: be placed in continuous fixed bed reactor by the sample of step (2), being warming up to 150 DEG C-400 DEG C under inert atmosphere, being passed through halide with halide volumn concentration in noble gas mixtures gaseous mixture is 1%-95%；Gas space velocity is 50h-1-1000 h-1；Processing pressure is to carry out under the conditions of 0.1MPa-0.5MPa, and the process time is 0.5h-8h.
The application of above-mentioned halide preparing isobutene catalyst, with halide as raw material, reaction temperature is 150 DEG C-350 DEG C, preferably 180 DEG C-300 DEG C, more preferably 200 DEG C-270 DEG C；Reaction pressure is 0.1MPa-5MPa(absolute pressure), preferably 0.1MPa-3MPa(absolute pressure)；Air speed is 50h-1-1000h-1, preferably 200h-1-500h-1, needing catalyst is carried out activation processing before charging, the content of halogen activated to catalyst is the 20%-90%, preferably 30%-80%, further preferred 40%-80% of total halogen content in reduction procatalyst.
In above-mentioned application, a kind of concrete activated process is as follows: by catalyzer temperature-elevating to 300 DEG C-600 DEG C under inert atmosphere, preferably 350 DEG C-550 DEG C；Then passing to air speed is 200h-1-2000h-1, preferably 500h-1-1000h-1Hydrogen or the mixed gas of hydrogen and noble gas, in 0.1MPa-0.5MPa(absolute pressure), preferably 0.1MPa-0.3MPa(absolute pressure), after processing 2h-16h, preferably 4h-8h, be down to reaction temperature and be passed through halide and react.In described gaseous mixture, hydrogen volume percentage composition is 10%-95%, preferably 30%-90%, more preferably 50%-90%.
In above-mentioned application, raw material can also be the mixed gas of halide and noble gas, and in mixed gas, the volumetric concentration of halide is 10%-90%, preferably 30%-80%.
Noble gas involved in above-mentioned application is the gas that nitrogen, argon, helium etc. do not occur chemical reaction under the conditions of involved in the present invention, preferably nitrogen.
In above-mentioned application, halide raw material can be a halide, methylene halide, three halides, preferably one bromomethane, methylene bromide, bromoform, more preferably one bromomethane.
In above-mentioned application, the reaction of halide preparing isobutene can be carried out, such as fixed bed, fluid bed, fixed fluidized bed, moving bed, the reactor of the form such as slurry bed system or ebullated bed, preferably fixed bed, fluidized-bed reactor in existing any form reactor.
Compared with prior art, bromomethane height can be optionally converted into isobutene. by the method that the present invention relates to.Active center on the carbon distribution meeting covering catalyst of generation in halide conversion process, blocking duct, stop reactant to contact with active center, thus cause the activity decrease of catalyst.After the inventive method introduces thorium auxiliary agent, reach to suppress the purpose of carbon distribution by the structure and surface nature improving catalyst.Catalyst from embodiments of the invention and comparative example it can be seen that after additive modification, has preferable carbon accumulation resisting ability.The present invention relates to bromomethane conversion preparing isobutene method for preparing catalyst simple, it is easy to industrialization.Bromomethane of the present invention converts preparing isobutene method and has reaction condition gentleness, selectivity of product advantages of higher, easily realizes industrialization, and application prospect is boundless.
Detailed description of the invention
Further illustrate technology contents and the effect of the present invention below in conjunction with embodiment, but be not intended to the present invention.
Embodiment
1
First weigh zinc nitrate to be dissolved in deionized water, use equi-volume impregnating to be carried on alumina support, 80 DEG C of dry 6h, 400 DEG C of roasting 6h, prepare ZnO/Al2O3；Then weigh thorium nitrate soluble in water, use equi-volume impregnating to be carried on ZnO/Al2O3On, 120 DEG C of dry 4h, 450 DEG C of roasting 6h, prepare ZnO-ThO2/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr2Content is 10.4%, and ZnO content is 1.2%, ThO2Content is 0.8%.In catalyst, less than 450 DEG C total acid contents are 0.82mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 58.11% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 50%, and reaction temperature is 230 DEG C, and reaction pressure is 1MPa(absolute pressure), air speed is 500h-1, it is passed through unstripped gas procatalyst and activates in a hydrogen atmosphere, reducing condition is 400 DEG C, 0.2MPa(absolute pressure), 1000h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 65.28%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio is 89.94%, and selective isobutene is 73.40%.
Embodiment
2
First weigh zinc nitrate to be dissolved in deionized water, use equi-volume impregnating to be carried on alumina support, 120 DEG C of dry 4h, 350 DEG C of roasting 8h, prepare ZnO/Al2O3；Then weigh thorium nitrate soluble in water, use equi-volume impregnating to be carried on ZnO/Al2O3On, 120 DEG C of dry 4h, 400 DEG C of roasting 8h, prepare ZnO-ThO2/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr2Content is 31.2%, and ZnO content is 3.7%, ThO2Content is 0.8%.In catalyst, less than 450 DEG C total acid contents are 0.91mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 50.19% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 51.7%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio is 97.24%, and selective isobutene is 83.48%.
Embodiment
3
First weigh zinc nitrate to be dissolved in deionized water, use equi-volume impregnating to be carried on alumina support, 100 DEG C of dry 8h, 400 DEG C of roasting 6h, prepare ZnO/Al2O3；Then weigh thorium nitrate soluble in water, use equi-volume impregnating to be carried on ZnO/Al2O3On, 120 DEG C of dry 4h, 350 DEG C of roasting 8h, prepare ZnO-ThO2/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr2Content is 41.9%, and ZnO content is 6.2%, ThO2Content is 0.8%.In catalyst, less than 450 DEG C total acid contents are 0.71mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 62.72% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 80%, and reaction temperature is 200 DEG C, and reaction pressure is 3MPa(absolute pressure), air speed is 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 50%, and reducing condition is 500 DEG C, 0.1MPa(absolute pressure), 500h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 45.66%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio is 93.62%, and selective isobutene is 80.98%.
Embodiment
4
First weigh zinc nitrate to be dissolved in deionized water, use equi-volume impregnating to be carried on alumina support, 110 DEG C of dry 10h, 450 DEG C of roasting 5h, prepare ZnO/Al2O3；Then weigh thorium nitrate soluble in water, use equi-volume impregnating to be carried on ZnO/Al2O3On, 120 DEG C of dry 4h, 500 DEG C of roasting 4h, prepare ZnO-ThO2/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr2Content is 28.4%, and ZnO content is 4.2%, ThO2Content is 0.5%.In catalyst, less than 450 DEG C total acid contents are 0.94mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 48.91% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 30%, and reaction temperature is 270 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 70%, and reducing condition is 350 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 6h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 55.9%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio is 95.49%, and selective isobutene is 81.16%.
Embodiment
5
First weigh zinc nitrate to be dissolved in deionized water, use equi-volume impregnating to be carried on alumina support, 90 DEG C of dry 4h, 500 DEG C of roasting 4h, prepare ZnO/Al2O3；Then weigh thorium nitrate soluble in water, use equi-volume impregnating to be carried on catalyst precarsor ZnO/Al2O3On, 120 DEG C of dry 4h, 520 DEG C of roasting 5h, prepare ZnO-ThO2/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr2Content is 27.5%, and ZnO content is 4.4%, ThO2Content is 1.0%.In catalyst, less than 450 DEG C total acid contents are 1.05mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 57.84% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane, and reaction temperature is 270 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 60%, and reducing condition is 550 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 8h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 40%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio is 95.92%, and selective isobutene is 80.54%.
Embodiment
6
First weigh zinc nitrate to be dissolved in deionized water, use equi-volume impregnating to be carried on alumina support, 120 DEG C of dry 12h, 380 DEG C of roasting 8h, prepare ZnO/Al2O3；Then weigh thorium nitrate soluble in water, use equi-volume impregnating to be carried on ZnO/Al2O3On, 120 DEG C of dry 4h, 380 DEG C of roasting 6h, prepare ZnO-ThO2/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr2Content is 31.6%, and ZnO content is 3.8%, ThO2Content is 5%.In catalyst, less than 450 DEG C total acid contents are 0.98mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 65.89% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 50%, and reaction temperature is 230 DEG C, and reaction pressure is 0.1MPa(absolute pressure), air speed is 500h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), 1000h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 56.46%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio is 99.26%, and selective isobutene is 65.79%.
Comparative example
1
Catalyst is prepared with embodiment 2.Evaluating catalyst condition is with embodiment 2, and difference is, does not carries out activation processing.After reacting one hour, sampling analysis.Bromomethane conversion ratio 5.06%, selective isobutene 0.
Comparative example
2
Catalyst is prepared with embodiment 2, and difference is, does not carries out halogenation treatment.Evaluating catalyst condition is with embodiment 2, after reacting one hour, and sampling analysis.Bromomethane conversion ratio 97.75%, selective isobutene 0.
Comparative example
3
Catalyst is prepared with embodiment 2.Evaluating catalyst condition is with embodiment 2, and difference is, is zinc by zinc bromide Restore All.After reacting one hour, sampling analysis.Bromomethane conversion ratio 2.78%, selective isobutene 0.
Embodiment
7
According to the catalyst of embodiment 2 preparation, respectively 230 DEG C, 300 DEG C, carry out reaction at 400 DEG C and investigate the carbon deposition quantity on catalyst, reaction condition is same as in Example 2.
When reaction temperature is 230 DEG C, carbon deposition quantity is 0.93%；When reaction temperature is 300 DEG C, carbon deposition quantity is 1.12%；When reaction temperature is 400 DEG C, carbon deposition quantity is 1.35%.
Claims (23)
1. a halide preparing isobutene catalyst with anti-carbon performance, it is characterised in that: in described catalyst, zinc oxide weight content is 0.5%-20%, and zinc halide weight content is 10%-50%, and thorium oxide weight content is 0.1%-20%, and surplus is alumina catalyst support.
Catalyst the most according to claim 1, it is characterised in that: in described catalyst, zinc oxide weight content is 1%-15%, and zinc halide weight content is 15%-45%, and thorium oxide weight content is 0.1%-15%.
Catalyst the most according to claim 1, it is characterised in that: in described catalyst, zinc oxide weight content is 1%-9%, and zinc halide weight content is 18%-39%, and thorium oxide weight content is 0.5%-5%.
Catalyst the most according to claim 1, it is characterised in that: in described halide preparing isobutene catalyst, less than 450 DEG C total acid content (NH3-TPD) it is 0.5mmol/g-1.3mmol/g, the acid content of 250 DEG C-350 DEG C accounts for the 20%-90% of less than 450 DEG C total acid contents.
Catalyst the most according to claim 1, it is characterised in that: in described halide preparing isobutene catalyst, less than 450 DEG C total acid content (NH3-TPD) it is 0.6mmol/g-1.2mmol/g, the acid content of 250 DEG C-350 DEG C accounts for the 30%-80% of less than 450 DEG C total acid contents.
Catalyst the most according to claim 1, it is characterised in that: in described halide preparing isobutene catalyst, less than 450 DEG C total acid content (NH3-TPD) it is 0.7mmol-1.1mmol/g, the acid content of 250 DEG C-350 DEG C accounts for the 40%-80% of less than 450 DEG C total acid contents.
7. the preparation of catalyst described in claim 1, it is characterised in that: include following preparation process:
(1) zinc precursor is dissolved in the water, uses equi-volume impregnating to be carried on carrier, after drying, roasting, prepare catalyst precarsor；
(2) thorium presoma is dissolved in ethanol, uses equi-volume impregnating to be carried on catalyst precarsor prepared by step (1), after drying, roasting, prepare the catalyst precarsor that thorium is modified；
(3) catalyst precarsor that step (2) gained thorium is modified is carried out halogenation treatment；Prepare halide preparing isobutene catalyst.
Method the most according to claim 7, it is characterised in that: described in step (1), zinc precursor is the one in nitrate, chlorate, acetate.
Method the most according to claim 7, it is characterised in that: described in step (1), baking temperature is 50 DEG C-200 DEG C, preferably 60 DEG C-150 DEG C, more preferably 80 DEG C-120 DEG C；Drying time is 1h-24h, preferably 4h-8h；Sintering temperature is 200 DEG C-800 DEG C, preferably 400 DEG C-600 DEG C；Roasting time is 1h-24h, preferably 4h-8h.
Method the most according to claim 7, it is characterised in that: described in step (2), thorium presoma is inorganic salt or organic salt, preferably nitrate, chlorate, acetate, more preferably nitrate.
11. methods according to claim 7, it is characterised in that: described in step (2), baking temperature is 50 DEG C-200 DEG C, preferably 60 DEG C-150 DEG C, more preferably 80 DEG C-120 DEG C；Drying time is 1h-24h, preferably 4h-8h；Can be vacuum drying time dry, it is also possible to for being dried under the conditions of inert gas shielding, it is also possible to be dried in air atmosphere.
12. sintering temperatures are 200 DEG C-800 DEG C, preferably 400 DEG C-600 DEG C；Roasting time is 1h-24h, preferably 4h-8h.
13. methods according to claim 7, it is characterized in that: described in step (3), halogenation treatment process is as follows: the sample of step (2) is placed in continuous fixed bed reactor, being warming up to 150 DEG C-400 DEG C under inert atmosphere, being passed through halide with halide volumn concentration in noble gas mixtures gaseous mixture is 1%-95%；Gas space velocity is 50h-1-1000
h-1；Processing pressure is 0.1MPa-0.5MPa, and the process time is 0.5h-8h.
14. methods according to claim 12, it is characterised in that: being warming up to 180 DEG C-350 DEG C under inert atmosphere, gas space velocity is 100h-1-500h-1；Processing pressure is 0.1MPa-0.3MPa, and the process time is 1h-4h.
Catalyst application in preparing isobutene described in 15. claim 1, it is characterised in that: with halide as raw material, reaction temperature is 150 DEG C-350 DEG C；Reaction pressure is 0.1MPa-5MPa；Air speed is 50h-1-1000h-1, needing before charging catalyst is carried out reduction treatment, the content of halogen being reduced in catalyst is the 20%-90% of total halogen content in reduction procatalyst.
16. application according to claim 14, it is characterised in that: reaction temperature is 180 DEG C-300 DEG C；Reaction pressure is 0.1MPa-3MPa；Air speed is 200h-1-500h-1, the content of halogen being reduced in catalyst is the 30%-80% of total halogen content in reduction procatalyst.
17. application according to claim 14, it is characterised in that: reduction treatment process is as follows: by catalyzer temperature-elevating to 300 DEG C-600 DEG C under inert atmosphere；Then passing to air speed is 200h-1-2000h-1Hydrogen or the mixed gas of hydrogen and noble gas, under 0.1MPa-0.5Mpa, process 2h-16h, be down to reaction temperature and be passed through halide and react, in gaseous mixture, hydrogen volume percentage composition is 10%-95%.
18. application according to claim 16, it is characterised in that: it is warming up to 350 DEG C-550 DEG C；Then passing to air speed is 500h-1-1000h-1Hydrogen or the mixed gas of hydrogen and noble gas, under 0.1MPa-0.3Mpa, process 4h-8h, in described gaseous mixture, hydrogen volume percentage composition is 30%-90%.
19. application according to claim 14, it is characterised in that: raw material is the mixed gas of halide and noble gas, and in mixed gas, the volumetric concentration of halide is 10%-90%, preferably 30%-80%.
20. application according to claim 14, it is characterised in that: noble gas is one or more in nitrogen, argon, helium.
21. application according to claim 14, it is characterised in that: halide raw material is one or more in a halide, methylene halide, three halides.
22. application according to claim 14, it is characterised in that: halide raw material is one or more in a bromomethane, methylene bromide, bromoform.
23. application according to claim 14, it is characterised in that: the reaction of halide preparing isobutene is carried out in fixed bed, fluid bed, fixed fluidized bed, moving bed, slurry bed system or fluidized bed reactor.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4154969A (en) * | 1977-03-24 | 1979-05-15 | Monsanto Company | Production of dihydroxydiphenyl alkanes |
| CN1502411A (en) * | 2002-11-20 | 2004-06-09 | ��Խ��ѧ��ҵ��ʽ���� | Zinc chloride-loaded support and method for producing the same |
| CN100582064C (en) * | 2006-03-20 | 2010-01-20 | 微宏科技（湖州）有限公司 | Flow process for synthesizing C3 to C13 high hydrocarbons by methane through non-synthetic gas method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4154969A (en) * | 1977-03-24 | 1979-05-15 | Monsanto Company | Production of dihydroxydiphenyl alkanes |
| CN1502411A (en) * | 2002-11-20 | 2004-06-09 | ��Խ��ѧ��ҵ��ʽ���� | Zinc chloride-loaded support and method for producing the same |
| CN100582064C (en) * | 2006-03-20 | 2010-01-20 | 微宏科技（湖州）有限公司 | Flow process for synthesizing C3 to C13 high hydrocarbons by methane through non-synthetic gas method |
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