CN106140203B - A kind of catalyst and its preparation method and application of C 4 olefin processed - Google Patents
A kind of catalyst and its preparation method and application of C 4 olefin processed Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- -1 C 4 olefin Chemical class 0.000 title abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 84
- 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 47
- 239000000243 solution Substances 0.000 claims abstract description 21
- KJJPLEZQSCZCKE-UHFFFAOYSA-N 2-aminopropane-1,3-diol Chemical compound OCC(N)CO KJJPLEZQSCZCKE-UHFFFAOYSA-N 0.000 claims abstract description 19
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 18
- 150000002696 manganese Chemical class 0.000 claims abstract description 17
- 230000032683 aging Effects 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 15
- 238000012545 processing Methods 0.000 claims abstract description 14
- 230000031709 bromination Effects 0.000 claims abstract description 12
- 238000005893 bromination reaction Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000010521 absorption reaction Methods 0.000 claims abstract description 11
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 11
- 239000007853 buffer solution Substances 0.000 claims abstract description 8
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 88
- 239000007789 gas Substances 0.000 claims description 80
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 72
- 239000001257 hydrogen Substances 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 35
- 230000004913 activation Effects 0.000 claims description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 30
- 229910052736 halogen Inorganic materials 0.000 claims description 26
- 150000002367 halogens Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 21
- 150000004820 halides Chemical class 0.000 claims description 17
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 12
- 239000008246 gaseous mixture Substances 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 2
- 235000005979 Citrus limon Nutrition 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- GZUXJHMPEANEGY-BJUDXGSMSA-N bromomethane Chemical group Br[11CH3] GZUXJHMPEANEGY-BJUDXGSMSA-N 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 53
- 229910052757 nitrogen Inorganic materials 0.000 description 27
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 20
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 10
- 235000019253 formic acid Nutrition 0.000 description 10
- 238000011068 loading method Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 8
- 229910021568 Manganese(II) bromide Inorganic materials 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 3
- 239000005695 Ammonium acetate Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 235000019257 ammonium acetate Nutrition 0.000 description 3
- 229940043376 ammonium acetate Drugs 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 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
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229950005228 bromoform Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 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
- 229910001509 metal bromide Inorganic materials 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 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
- 230000009466 transformation Effects 0.000 description 2
- DOGCTUGYGZGSFX-UHFFFAOYSA-N 1-aminopropane-1,3-diol Chemical compound NC(O)CCO DOGCTUGYGZGSFX-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 206010013786 Dry skin Diseases 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
- 230000009471 action Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XDYHDLLKHFVVSE-UHFFFAOYSA-N hydrate;dihydrobromide Chemical compound O.Br.Br XDYHDLLKHFVVSE-UHFFFAOYSA-N 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002002 slurry Substances 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
- 238000001291 vacuum drying Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of catalyst and its preparation method and application of C 4 olefin processed.The catalyst is prepared using following steps: (1) alumina support is saturated the buffer solution of dipping ammonium salt-containing in equal volume, dry 0.5-1h after dipping at 95-110 DEG C immediately, the adsorbance of the dry buffer solution to ammonium salt-containing is the 30-60% of alumina support saturated absorption amount of solution, and modified aluminium oxide supports are then made after aging, drying, roasting；(2) the modified aluminium oxide supports saturation of step (1) preparation impregnates manganese salt solution and is dried, roasts, the 2- amino-1,3-propanediol for being 2-15% containing mass fraction in the manganese salt solution；(3) carrying out bromination processing to the material after step (2) roasting makes manganese oxide weight content 0.5%-5%, preferably 1%-3% in catalyst；Manganous bromide weight content is 5%-40%, preferably 10%-30%.The catalyst can significantly improve the selectivity of isobutene.
Description
Technical field
The present invention relates to a kind of catalyst and its preparation method and application of C 4 olefin processed, relate in particular to it is a kind of with
Bromomethane is the catalyst and its preparation method and application of the highly selective preparing isobutene of raw material.
Background technique
Isobutene is a kind of important basic organic chemical industry raw material, and derived product is numerous, and vertical industry chain is complicated, is disappeared
Take structure in diversified trend.A variety of high value-added products can be prepared by raw material of isobutene, such as: butyl rubber, gather it is different
A variety of Organic Chemicals such as butylene, methyl tertiary butyl ether(MTBE), isoprene and organic glass and fine chemistry product.Due to isobutyl
The market scale of alkene downstream product constantly expands, and imbalance between supply and demand will be protruded gradually, especially increasingly depleted in petroleum resources
Under background, the yield of isobutene has become the critical bottleneck for restricting downstream industry development.Therefore, the isobutyl of Non oil-based route is developed
Alkene preparation route is extremely urgent.
Methane is the main component of natural gas, therefore methane trans-utilization important grinding of just becoming in gas chemical industry's technology
Study carefully content.Especially in recent years, under the overall background of shale gas development and utilization, if it is possible to realize from methane and produce isobutyl
Alkene will provide a new approach to obtain isobutene.But methane property is stablized, and it is not easily-activated, become methane chemical industry benefit
Bottleneck.Domestic and international many researchers carry out methane activation, Study on Transformation one after another, and among these, methane is through halogen functional groupization
The technology converted again afterwards is expected to become an important breakthrough mouth for solving methane transformation technology problem.
Many chemical products can be prepared from halide.Chinese patent CN 101041609A, CN 101284232A
Disclose it is a kind of by methane in oxygen and HBr/H2Bromomethane is converted under the action of O, then bromomethane further reacts
The method for generating C3 ~ C13 mixing high-carbon hydrocarbon, the hydrocarbon selective of C5 or more are 70%.Wherein, HBr is used in first reactor
It in methane bromination, is then discharged in second reactor, is used further to after recovered in back reaction, realizes the circulation of HBr
It uses.(CN 102527427A, Jieli He, Ting Xu, Zhihui Wang, the et.al. Angew. Chem. such as Wang Ye
Int. Ed. 2012,51,2438-2442) disclose the modified molecular sieve catalyst and its system of a kind of halide propylene
Preparation Method.By using fluorochemical moditied processing molecular sieve, a kind of catalysis containing appropriate microporous structure and acidity is obtained
Agent, the catalyst can effectively be catalyzed the reaction that halide is converted into propylene.Prepared catalyst is converted in bromomethane
One way bromomethane conversion ratio is 35 ~ 99% in the reaction of propylene processed, and the selectivity of propylene is 27 ~ 70%；In chloromethanes conversion system third
One way methyl chloride conversion rate is 30 ~ 99% in the reaction of alkene, 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 generating bromo-hydrocarbons with the alkane reaction in bromine and natural gas, is then urged in metal oxide
Dimethyl ether, methanol and metal bromide are converted by bromo-hydrocarbons in agent, obtains metal oxygen after metal bromide oxygen recovery
Compound simultaneously releases simple substance bromine, completes the circulation of bromine.
Currently, being mainly methanol, dimethyl ether, acetic acid, high-carbon about purpose product in the existing literature of halide conversion
Hydro carbons, ethylene and propylene etc..In the technology using the low-carbon alkene compared with high added value as target product, single selectivity of product
It is not high, not yet find the relevant report of bromomethane high selectivity isobutene.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of urging using bromomethane as the highly selective preparing isobutene of raw material
Agent and the preparation method and application thereof.
A kind of preparation method of bromomethane preparing isobutene catalyst, characterized by the following steps: (1) aluminium oxide
Carrier is saturated the buffer solution of dipping ammonium salt-containing in equal volume, the dry 0.5-1h at 95-110 DEG C immediately after dipping, dry to containing
The adsorbance of the buffer solution of ammonium salt is the 30-60% of alumina support saturated absorption amount of solution, then through aging, drying, roasting
Modified aluminium oxide supports are made afterwards；(2) the modified aluminium oxide supports saturation of step (1) preparation impregnates manganese salt solution and is done
Dry, roasting, the 2- amino-1,3-propanediol for being 2-15% containing mass fraction in the manganese salt solution；(3) step (2) are roasted
Material afterwards, which carries out bromination processing, makes manganese oxide weight content 0.5%-5% in catalyst；Manganous bromide weight content is 5%-40%.
In the preparation method of above-mentioned bromomethane preparing isobutene catalyst, the buffered aqueous solution ammonium salt of ammonium salt-containing can in rapid (1)
To be selected from one or more of ammonium acetate, ammonium formate, ammonium carbonate, ammonium hydrogen carbonate etc..The weight of ammonium salt is dense in buffer solution
Degree is 1%-35%, preferably 5%-20%.Aging temperature is 50-95 DEG C, preferably 60 ~ 80 DEG C, ageing time 0.5-10h, excellent
Select 2-5h.Drying temperature is 90-150 DEG C, drying time 0.5-36h after aging, the dry 8-24h preferably at 100-120 DEG C.
Roasting roasts 2-15 hours at 280-500 DEG C, roasts 3-5 hours preferably at 300-450 DEG C.
In the preparation method of above-mentioned bromomethane preparing isobutene catalyst, the alumina support can use existing aluminium oxide
Product can also be prepared by method well known to those skilled in the art.Carrier can be made or choose according to the needs of use suitable
Suitable particle shape, such as bar shaped, piece shape, cylindricality, spherical shape is made.Forming can be carried out by this field general knowledge.
Drying condition is -150 DEG C of temperature 60 C in the preparation method step (2) of above-mentioned bromomethane preparing isobutene catalyst,
Preferably 80 DEG C -120 DEG C；Time is 1h-24h, preferably 4h-8h；It can be vacuum drying when dry, or indifferent gas
It is dry under body protective condition, it can also dry in air atmosphere.The roasting condition is 300 DEG C -600 DEG C of temperature, preferably
400℃-500℃；Time is 1h-24h, preferably 4h-8h；It can be to be roasted under the conditions of inert gas shielding when roasting, it can also
To roast in air atmosphere.
In the above method, manganese salt can be inorganic salts, or organic salt, preferably nitrate, hydrochloride, acetic acid
One or more of salt, citrate.
The processing of bromination described in the preparation method step (3) of above-mentioned bromomethane preparing isobutene catalyst, refers to using gas phase
Bromine-containing compound handles the sample of load manganese oxide.Bromine-containing compound refers to bromomethane, methylene bromide, in bromoform
One or more, preferably bromomethane.Bromine can also be carried out using the mixed gas of gas phase bromine-containing compound and inert gas
Change processing, when being handled using mixed gas bromination, bromomethane volumetric concentration is not less than 20%, preferably not less than 30%.Specifically
Bromination process is as follows: the sample for loading manganese oxide being placed in continuous fixed bed reactor, is warming up to 150 under inert atmosphere
DEG C -400 DEG C, preferably 180 DEG C -350 DEG C, more preferably 200 DEG C -300 DEG C, are passed through gas phase bromine-containing compound gas, gas space
Speed is 50h-1-1000 h-1, preferably 100h-1-500h-1；Can be carried out in normal pressure when processing, can also under a certain pressure into
Row, system pressure are 0.1MPa-0.5MPa(absolute pressure), preferably 0.1MPa-0.3MPa(absolute pressure), the processing time is 0.5h-8h,
It is preferred that 1h-4h.
Inert gas involved in the preparation method of above-mentioned bromomethane preparing isobutene catalyst is nitrogen, argon gas, helium
Deng the gas not chemically reacted under the conditions of involved in the present invention, preferably nitrogen.
The bromomethane preparing isobutene catalyst, manganese oxide weight content is 0.5%-5%, preferably 1%-3% in catalyst；Bromine
Change manganese weight content is 5%-40%, preferably 10%-30%；Cerium oxide weight content is 0.1%-2%, preferably 0.5%-1.5%；Oxidation
Alumina supporter weight content 60%-95%, preferably 65%-90%.
Application of the above-mentioned catalyst in preparing isobutene, including hydrogen reducing activation is carried out to catalyst, make in catalyst
Content of halogen be the 20%-90% for restoring total halogen content in procatalyst, then make halide and above-mentioned hydrogen reducing living
Catalyst contact after change, to prepare isobutene.
In above-mentioned application, the condition of the hydrogen reducing activation is urged before the content of halogen in catalyst is preferably restored
The 30%-80% of total halogen content in agent, further preferred 40%-80%.
In above-mentioned application, the mode of hydrogen reducing activation include under an inert atmosphere by catalyzer temperature-elevating to 300 DEG C-
600℃；Then passing to air speed is 200h-1-2000h-1Hydrogen or hydrogen and inert gas mixed gas, in 0.1MPa-
0.5MPa keeps 2h-16h, and hydrogen volume percentage composition is 10%-95% in mixed gas；Preferably, it is warming up to 350 DEG C -550
℃；Then passing to air speed is 500h-1-1000h-1Hydrogen or hydrogen and inert gas mixed gas, in 0.1MPa-
0.3MPa keeps 4h-8h, and hydrogen volume percentage composition is 30%-90% in the mixed gas.
The application of above-mentioned catalyst further includes that halide contacts acquisition isobutene with catalyst.The condition of the contact
It is 150 DEG C -350 DEG C including reaction temperature；Reaction pressure is 0.1MPa-5MPa；Air speed is 50h-1-1000h-1；It is highly preferred that
Reaction temperature is 180 DEG C -300 DEG C more preferably 200-270 DEG C；Reaction pressure is 0.1MPa-3MPa；Air speed is 200h-1-
500h-1。
In above-mentioned application, the halide can be one of a halide, methylene halide, three halides
Or a variety of, preferably one of bromomethane, methylene bromide, bromoform or a variety of, more preferably bromomethane.
By catalyzer temperature-elevating to 300 DEG C -600 DEG C under one of above-mentioned application specific embodiment, including inert atmosphere,
Preferably 350 DEG C -550 DEG C；Then passing to air speed is 200h-1-2000h-1, preferably 500h-1-1000h-1Hydrogen and inertia
The mixed gas of gas, in 0.1MPa-0.5MPa(absolute pressure), preferably 0.1MPa-0.3MPa(absolute pressure) processing 2h-16h, preferably
After 4h-8h, it is down to reaction temperature and is passed through halide and reacted.Hydrogen volume percentage composition is 10%- in the gaseous mixture
95%, preferably 30%-90%, more preferably 50%-90%.
In above-mentioned application, raw material may be the mixed gas of halide and inert gas, halogenated first in mixed gas
The volumetric concentration of alkane is 10%-90%, preferably 30%-80%.
Inert gas involved in above-mentioned application is that nitrogen, argon gas, helium etc. are not sent out under the conditions of involved in the present invention
The gas of biochemical reaction, preferably nitrogen.
In above-mentioned application, the reaction of halide preparing isobutene can carry out in existing any form reactor, such as fixed
Bed, fluidized bed, fixed fluidized bed, moving bed, the reactor of the forms such as slurry bed system or ebullated bed, preferably fixed bed, fluidized bed
Reactor.
Compared with prior art, method of the present invention can by bromomethane it is highly selective be converted into isobutene.?
Using uneven modified method in the method for the present invention, modified solution makes it be concentrated mainly on the inside of carrier after partially evaporating, makes
The inside and outside property of catalyst generates difference, improves the catalytic activity of catalytic inner, it is suppressed that the isobutene of diffusion carries out again
Reaction.The dispersion degree that can be improved active component using the manganese salt solution that joined the amino-1,3-propanediol containing 2-, is prepared small
The active component Mn catalyst of crystal grain, to significantly improve the selectivity of low-carbon alkene.Bromomethane is carried out by the method for the present invention to turn
Change preparing isobutene reaction, 50% or more bromomethane conversion ratio, 60% or more selective isobutene.The present invention relates to bromomethane conversions to make
Isobutene catalyst preparation method is simple, is easy to industrialize.Bromomethane conversion preparing isobutene method of the present invention has reaction condition
Mildly, the advantages that selectivity of product is high, industrialization easy to accomplish, application prospect are boundless.
Specific embodiment
Technology contents and effect of the invention are further illustrated below with reference to embodiment, but are not so limited the present invention.
Embodiment 1
Weigh commercial alumina (Kong Rongwei 0.96ml/g, specific surface area 286.81m2/ g, saturated water adsorptive value 145ml/
G is provided by Fushun branch company of Sinopec catalyst Co., Ltd, and following embodiment and comparative example use the aluminium oxide), it will
The ammonium carbonate solution saturation spray oxide impregnation aluminium that mass concentration is 5%, after the dry 1h at 95 DEG C immediately, dry system
The adsorbance of ammonium carbonate solution is the 60% of alumina support saturated absorption amount of solution, and aging 7h at 60 DEG C is done in 100 DEG C
Dry 24 hours, then in 300 DEG C of roastings, 5 hours obtained modified aluminium oxide supports.It weighs appropriate manganese nitrate and is dissolved in deionized water, add
Entering 2- amino-1,3-propanediol makes the mass fraction 2% of 2- amino-1,3-propanediol in the solution, the bodies such as manganese salt solution use
Product infusion process is carried on above-mentioned alumina support, and catalyst precarsor is made in 100 DEG C of dry 6h, 450 DEG C of roasting 6h.It will catalysis
Agent precursor is placed in continuous fixed bed reactor, handles catalyst precarsor, bromine using the mixed gas of bromomethane and nitrogen
Volume percent methane is 60%, and treatment conditions are 250 DEG C, 0.2MPa(absolute pressure), 300h-1, time 2h, obtained bromomethane isobutyl
Alkene catalyst, is denoted as C-1.Obtain catalyst MnBr2Weight content is 18%, MnO weight content in terms of oxide in terms of bromide
It is 2%.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 70% in mixed gas, activation condition
It is 450 DEG C, 0.2MPa(absolute pressure), 750h-1, activation time 6h；Restoring the content of halogen in rear catalyst is reduction procatalyst
The 71.91% of middle total halogen content.
After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein
Bromomethane volume content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed 350h-1.Stable reaction
After one hour, sampling analysis.Reaction result is shown in Table 1.
Embodiment 2
Weigh commercial alumina, by mass concentration be 20% ammonium acetate aqueous solution saturation spray oxide impregnation aluminium, after stand
The dry 0.5h i.e. at 110 DEG C, the dry adsorbance to ammonium acetate aqueous solution are alumina support saturated absorption amount of solution
40%, it is 8 hours dry in 120 DEG C aging 4 hours at 80 DEG C, modified aluminas load then roast 3 hours to obtain in 400 DEG C
Body.It weighs appropriate manganese nitrate and is dissolved in deionized water, 2- amino-1,3-propanediol, which is added, makes 2- amino-1,3-propanediol in solution
In mass fraction be 15%, manganese salt solution is carried on above-mentioned alumina support using equi-volume impregnating, 100 DEG C of dry 6h,
Catalyst precarsor is made in 400 DEG C of roasting 8h.Catalyst precarsor is placed in continuous fixed bed reactor, bromomethane is used
Catalyst precarsor is handled with the mixed gas of nitrogen, bromomethane volumetric concentration is 60%, and treatment conditions are 250 DEG C, and 0.2MPa(is exhausted
Pressure), 300h-1, time 2h, be made bromomethane preparing isobutene catalyst, be denoted as C-2.Obtain catalyst MnBr2It is counted weight with bromide
It is 2% that amount content, which is 18%, MnO weight content in terms of oxide,.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 70% in mixed gas, activation condition
It is 450 DEG C, 0.2MPa(absolute pressure), 750h-1, activation time 6h；Restoring the content of halogen in rear catalyst is reduction procatalyst
The 78.37% of middle total halogen content.
After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein
Bromomethane volume content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed 350h-1.Stable reaction
After one hour, sampling analysis.Reaction result is shown in Table 1.
Embodiment 3
Commercial alumina is weighed, is 20% ammonium bicarbonate aqueous solution saturation spray oxide impregnation aluminium by mass concentration, after
The dry 0.5h at 110 DEG C, the dry adsorbance to ammonium bicarbonate aqueous solution are alumina support saturated absorption amount of solution immediately
40%, it is 8 hours dry in 120 DEG C aging 4 hours at 80 DEG C, then roast in 400 DEG C 3 hours and obtains modified aluminas
Carrier.It weighs appropriate manganese nitrate and is dissolved in deionized water, 2- amino-1,3-propanediol, which is added, makes 2- amino-1,3-propanediol molten
Mass fraction in liquid is 10%, and manganese salt solution is carried on above-mentioned alumina support using equi-volume impregnating, 120 DEG C of dryings
Catalyst precarsor is made in 4h, 500 DEG C of roasting 4h.Catalyst precarsor is placed in continuous fixed bed reactor, bromine first is used
The mixed gas of alkane and nitrogen handles catalyst precarsor, and bromomethane volumetric concentration is 60%, and treatment conditions are 250 DEG C, 0.2MPa
(absolute pressure), 300h-1, time 2h, be made bromomethane preparing isobutene catalyst, be denoted as C-3.Obtain catalyst MnBr2With bromide
It is 2% that meter weight content, which is 18%, MnO weight content in terms of oxide,.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 70% in mixed gas, activation condition
It is 450 DEG C, 0.2MPa(absolute pressure), 750h-1, activation time 6h；Restoring the content of halogen in rear catalyst is reduction procatalyst
The 56.97% of middle total halogen content.
After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein
Bromomethane volume content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 0.2MPa(absolute pressure), air speed 350h-1.Reaction is steady
After one hour fixed, sampling analysis.Reaction result is shown in Table 1.
Embodiment 4
Weigh commercial alumina, by mass concentration be 20% formic acid aqueous ammonium saturation spray oxide impregnation aluminium, after stand
The dry 0.5h i.e. at 110 DEG C, the dry adsorbance to formic acid aqueous ammonium are alumina support saturated absorption amount of solution
40%, it is 8 hours dry in 120 DEG C aging 4 hours at 80 DEG C, modified aluminas load then roast 3 hours to obtain in 400 DEG C
Body.It weighs appropriate manganese nitrate and is dissolved in deionized water, 2- amino-1,3-propanediol, which is added, makes 2- amino-1,3-propanediol in solution
In mass fraction be 5%, manganese salt solution is carried on above-mentioned alumina support using equi-volume impregnating, 100 DEG C of dry 6h,
Catalyst precarsor is made in 450 DEG C of roasting 6h.Catalyst precarsor is placed in continuous fixed bed reactor, bromomethane is used
Catalyst precarsor is handled with the mixed gas of nitrogen, bromomethane volumetric concentration is 30%, and treatment conditions are 250 DEG C, and 0.2MPa(is exhausted
Pressure), 300h-1, time 2h, be made bromomethane preparing isobutene catalyst, be denoted as C-4.Obtain catalyst MnBr2It is counted weight with bromide
It is 3% that amount content, which is 15%, MnO weight content in terms of oxide,.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 50% in mixed gas, activation condition
It is 550 DEG C, 0.1MPa(absolute pressure), 1000h-1, activation time 4h；Restoring the content of halogen in rear catalyst is reduction procatalyst
The 68.21% of middle total halogen content.
After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein
Bromomethane volume content is 30%, and reaction temperature is 250 DEG C, and reaction pressure is 3MPa(absolute pressure), air speed 500h-1.Stable reaction
After one hour, sampling analysis.Reaction result is shown in Table 1.
Embodiment 5
Weigh commercial alumina, by mass concentration be 20% formic acid aqueous ammonium saturation spray oxide impregnation aluminium, after stand
The dry 0.5h i.e. at 110 DEG C, the dry adsorbance to formic acid aqueous ammonium are alumina support saturated absorption amount of solution
40%, it is 8 hours dry in 120 DEG C aging 4 hours at 80 DEG C, modified aluminas load then roast 3 hours to obtain in 400 DEG C
Body.It weighs appropriate manganese nitrate and is dissolved in deionized water, 2- amino-1,3-propanediol, which is added, makes 2- amino-1,3-propanediol in solution
In mass fraction be 10%, manganese salt solution is carried on above-mentioned alumina support using equi-volume impregnating, 100 DEG C of dry 6h,
Catalyst precarsor is made in 450 DEG C of roasting 6h.Catalyst precarsor is placed in continuous fixed bed reactor, bromomethane is used
Gas processing catalyst precursor, treatment conditions are 250 DEG C, 0.2MPa(absolute pressure), 300h-1, time 2h, obtained bromomethane isobutyl
Alkene catalyst, is denoted as C-5.Obtain catalyst MnBr2Weight content is 24%, MnO weight content in terms of oxide in terms of bromide
It is 2%.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 90% in mixed gas, activation condition
It is 350 DEG C, 0.3MPa(absolute pressure), 500h-1, activation time 8h；Restoring the content of halogen in rear catalyst is reduction procatalyst
The 58.56% of middle total halogen content.
After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein
Bromomethane volume content is 80%, and reaction temperature is 210 DEG C, and reaction pressure is 0.1MPa(absolute pressure), air speed 200h-1.Reaction is steady
After one hour fixed, sampling analysis.Reaction result is shown in Table 1.
Embodiment 6
Weigh commercial alumina, by mass concentration be 20% formic acid aqueous ammonium saturation spray oxide impregnation aluminium, after stand
The dry 0.5h i.e. at 110 DEG C, the dry adsorbance to formic acid aqueous ammonium are alumina support saturated absorption amount of solution
40%, it is 8 hours dry in 120 DEG C aging 4 hours at 80 DEG C, modified aluminas load then roast 3 hours to obtain in 400 DEG C
Body.It weighs appropriate manganese nitrate and is dissolved in deionized water, 2- amino-1,3-propanediol, which is added, makes 2- amino-1,3-propanediol in solution
In mass fraction be 6%, manganese salt solution is carried on above-mentioned alumina support using equi-volume impregnating, 100 DEG C of dry 6h,
Catalyst precarsor is made in 450 DEG C of roasting 6h.Catalyst precarsor is placed in continuous fixed bed reactor, bromomethane is used
Catalyst precarsor is handled with the mixed gas of nitrogen, bromomethane volumetric concentration is 60%, and treatment conditions are 250 DEG C, and 0.2MPa(is exhausted
Pressure), 300h-1, time 2h, be made bromomethane preparing isobutene catalyst, be denoted as C-6.Obtain catalyst MnBr2It is counted weight with bromide
It is 1% that amount content, which is 30%, MnO weight content in terms of oxide,.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 70% in mixed gas, activation condition
It is 450 DEG C, 0.2MPa(absolute pressure), 750h-1, activation time 6h；Restoring the content of halogen in rear catalyst is reduction procatalyst
The 78.89% of middle total halogen content.
After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein
Bromomethane volume content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed 350h-1.Stable reaction
After one hour, sampling analysis.Reaction result is shown in Table 1.
Embodiment 7
Weigh commercial alumina, by mass concentration be 20% formic acid aqueous ammonium saturation spray oxide impregnation aluminium, after stand
The dry 0.5h i.e. at 110 DEG C, the dry adsorbance to formic acid aqueous ammonium are alumina support saturated absorption amount of solution
40%, it is 8 hours dry in 120 DEG C aging 4 hours at 80 DEG C, modified aluminas load then roast 3 hours to obtain in 400 DEG C
Body.It weighs appropriate manganese nitrate and is dissolved in deionized water, 2- amino-1,3-propanediol, which is added, makes 2- amino-1,3-propanediol in solution
In mass fraction be 10%, manganese salt solution is carried on above-mentioned alumina support using equi-volume impregnating, 100 DEG C of dry 6h,
Catalyst precarsor is made in 450 DEG C of roasting 6h.Catalyst precarsor is placed in continuous fixed bed reactor, bromomethane is used
Catalyst precarsor is handled with the mixed gas of nitrogen, bromomethane volumetric concentration is 60%, and treatment conditions are 250 DEG C, and 0.2MPa(is exhausted
Pressure), 300h-1, time 2h, be made bromomethane preparing isobutene catalyst, be denoted as C-7.Obtain catalyst MnBr2It is counted weight with bromide
It is 1% that amount content, which is 10%, MnO weight content in terms of oxide,.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 70% in mixed gas, activation condition
It is 450 DEG C, 0.2MPa(absolute pressure), 750h-1, activation time 6h；Restoring the content of halogen in rear catalyst is reduction procatalyst
The 69.21% of middle total halogen content.
After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein
Bromomethane volume content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed 350h-1.Stable reaction
After one hour, sampling analysis.Reaction result is shown in Table 1.
Embodiment 8
Weigh commercial alumina, by mass concentration be 20% formic acid aqueous ammonium saturation spray oxide impregnation aluminium, after stand
The dry 0.5h i.e. at 110 DEG C, the dry adsorbance to formic acid aqueous ammonium are alumina support saturated absorption amount of solution
40%, it is 8 hours dry in 120 DEG C aging 4 hours at 80 DEG C, modified aluminas load then roast 3 hours to obtain in 400 DEG C
Body.It weighs appropriate manganese nitrate and is dissolved in deionized water, 2- amino-1,3-propanediol, which is added, makes 2- amino-1,3-propanediol in solution
In mass fraction be 5%, manganese salt solution is carried on above-mentioned alumina support using equi-volume impregnating, 100 DEG C of dry 6h,
Catalyst precarsor is made in 450 DEG C of roasting 6h.Catalyst precarsor is placed in continuous fixed bed reactor, bromomethane is used
Catalyst precarsor is handled with the mixed gas of nitrogen, bromomethane volumetric concentration is 60%, and treatment conditions are 200 DEG C, and 0.3MPa(is exhausted
Pressure), 500h-1, time 1h, be made bromomethane preparing isobutene catalyst, be denoted as C-8.Obtain catalyst MnBr2It is counted weight with bromide
It is 2% that amount content, which is 18%, MnO weight content in terms of oxide,.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g,
Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 70% in mixed gas, activation condition
It is 450 DEG C, 0.2MPa(absolute pressure), 750h-1, activation time 6h；Restoring the content of halogen in rear catalyst is reduction procatalyst
The 67.41% of middle total halogen content.
After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein
Bromomethane volume content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed 350h-1.Stable reaction
After one hour, sampling analysis.Reaction result is shown in Table 1.
Comparative example 1
Catalyst is prepared by embodiment 1, does not use bromination to handle in preparation process.Evaluation condition is the same as embodiment 1.Reaction knot
Fruit is shown in Table 1.
Comparative example 2
Take catalyst C-1 without reduction activation, directly progress bromomethane conversion reaction.Reaction condition is the same as embodiment 1.Reaction
It the results are shown in Table 1.
Comparative example 3
With embodiment 1, the difference is that manganous bromide restores completely during carrying out bromomethane conversion reaction.
Reaction result is shown in Table 1.
1 catalyst reaction performance of table
Claims (21)
1. a kind of preparation method of bromomethane preparing isobutene catalyst, characterized by the following steps: (1) carrying alumina
Body is saturated the buffer solution of dipping ammonium salt-containing in equal volume, and the drying 0.5-1h at 95-110 DEG C, drying immediately extremely contains ammonium after dipping
The adsorbance of the buffer solution of salt is the 30-60% of alumina support saturated absorption amount of solution, then after aging, drying, roasting
Modified aluminium oxide supports are made；(2) step (1) preparation modified aluminium oxide supports saturation dipping manganese salt solution and be dried,
It roasts, the 2- amino-1,3-propanediol for being 2-15% containing mass fraction in the manganese salt solution；(3) after to step (2) roasting
Material carry out bromination processing make manganese oxide weight content 0.5%-5% in catalyst；Manganous bromide weight content is 5%-40%.
2. according to the method described in claim 1, it is characterized by: the buffered aqueous solution ammonium salt of ammonium salt-containing is vinegar in step (1)
One or more of sour ammonium, ammonium formate, ammonium carbonate, ammonium hydrogen carbonate；The weight concentration of ammonium salt is 1%-35% in buffer solution；Always
Changing temperature is 50-95 DEG C, ageing time 0.5-10h, and drying temperature is 90-150 DEG C, drying time 0.5-36h after aging,
Roasting roasts 2-15 hours at 280-500 DEG C.
3. according to the method described in claim 1, it is characterized by: step (2) drying condition is -150 DEG C of temperature 60 C, when
Between be 1h-24h, roasting condition is 300 DEG C -600 DEG C of temperature, time 1h-24h.
4. according to the method described in claim 1, it is characterized by: step (2) manganese salt is nitrate, hydrochloride, acetate, lemon
One or more of lemon hydrochlorate.
5. according to the method described in claim 1, it is characterized by: the processing of bromination described in step (3), is referred to and is contained using gas phase
Bromine compounds handles the sample of load manganese oxide.
6. according to the method described in claim 5, it is characterized by: bromine-containing compound refers to bromomethane, methylene bromide, tribromo first
One or more of alkane.
7. according to the method described in claim 1, it is characterized by: using gas phase bromine-containing compound and indifferent gas in step (3)
The mixed gas of body carries out bromination processing, and bromomethane volumetric concentration is not less than 20%.
8. according to the method described in claim 1, it is characterized by: specific bromination process is as follows in step (3): load is aoxidized
The sample of manganese is placed in continuous fixed bed reactor, and 150 DEG C -400 DEG C are warming up under inert atmosphere, is passed through gas phase containing bromination
Close object gas, gas space velocity 50h-1-1000 h-1；System pressure is 0.1MPa-0.5MPa, and the processing time is 0.5h-8h.
9. according to the method described in claim 8, being passed through gas phase it is characterized by: be warming up to 180 DEG C -350 DEG C under inert atmosphere
Bromine-containing compound gas, gas space velocity 100h-1-500h-1；System pressure is 0.1MPa-0.3MPa, and the processing time is 1h-
4h。
10. the catalyst of claim 1 to 9 either method preparation, it is characterised in that: manganese oxide weight content is in catalyst
0.5%-5%；Manganous bromide weight content is 5%-40%.
11. catalyst according to claim 10, it is characterised in that: manganese oxide weight content is 1%-3%；Manganous bromide weight
Content is 10%-30%.
12. application of any catalyst of claim 10-11 in preparing isobutene, it is characterised in that: including being carried out to catalyst
Hydrogen reducing activation makes the content of halogen in catalyst restore the 20%-90% of total halogen content in procatalyst, then makes halogen
It is contacted for methane with the catalyst after the activation of above-mentioned hydrogen reducing, to prepare isobutene.
13. application according to claim 12, it is characterised in that: the condition of the hydrogen reducing activation makes in catalyst
Content of halogen be restore procatalyst in total halogen content 30%-80%.
14. application according to claim 12, it is characterised in that: the mode of the hydrogen reducing activation is included in indifferent gas
By catalyzer temperature-elevating to 300 DEG C -600 DEG C under atmosphere；Then passing to air speed is 200h-1-2000h-1Hydrogen or hydrogen and indifferent gas
The mixed gas of body keeps 2h-16h in 0.1MPa-0.5MPa, and hydrogen volume percentage composition is 10%-95% in mixed gas.
15. application according to claim 14, it is characterised in that: be warming up to 350 DEG C -550 DEG C；Then passing to air speed is
500h-1-1000h-1Hydrogen or hydrogen and inert gas mixed gas, keep 4h-8h in 0.1MPa-0.3MPa, it is described mixed
Closing hydrogen volume percentage composition in gas is 30%-90%.
16. application according to claim 12, it is characterised in that: the condition of the contact include reaction temperature be 150 DEG C-
350℃；Reaction pressure is 0.1MPa-5MPa；Air speed is 50h-1-1000h-1。
17. application according to claim 16, 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。
18. application according to claim 12, it is characterised in that: the halide is a halide, dihalo first
One of alkane, three halides are a variety of.
19. application according to claim 12, it is characterised in that: the halide is bromomethane, methylene bromide, tribromo
One of methane is a variety of.
20. application according to claim 12, it is characterised in that: including under inert atmosphere by catalyzer temperature-elevating to 300 DEG C-
600℃；Then passing to air speed is 200h-1-2000h-1Hydrogen and inert gas mixed gas, at 0.1MPa-0.5MPa
After managing 2h-16h, it is down to reaction temperature and is passed through halide and reacted, hydrogen volume percentage composition is in the gaseous mixture
10%-95%。
21. application according to claim 20, it is characterised in that: including under inert atmosphere by catalyzer temperature-elevating to 350 DEG C-
550℃；Then passing to air speed is 500h-1-1000h-1Hydrogen and inert gas mixed gas, at 0.1MPa-0.3MPa
It after managing 4h-8h, is down to reaction temperature and is passed through halide and reacted, hydrogen volume percentage composition is 30%- in the gaseous mixture
90%。
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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 |
| CN1237038C (en) * | 2000-06-30 | 2006-01-18 | Dsmip资产有限公司 | Isomerization of pentol |
| 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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2015
- 2015-03-27 CN CN201510135826.3A patent/CN106140203B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4154969A (en) * | 1977-03-24 | 1979-05-15 | Monsanto Company | Production of dihydroxydiphenyl alkanes |
| CN1237038C (en) * | 2000-06-30 | 2006-01-18 | Dsmip资产有限公司 | Isomerization of pentol |
| 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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