CN106140274B - A kind of catalyst of the highly selective preparing isobutene of bromomethane and preparation method thereof - Google Patents
A kind of catalyst of the highly selective preparing isobutene of bromomethane and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses catalyst of the highly selective preparing isobutene of a kind of bromomethane and preparation method thereof.Preparation method includes following process：（1）Ammonium molybdate and ammonium tungstate is soluble in water, obtain solution A；（2）Carrier is added to step（1）In obtained solution A, after aging, drying, calcination process, catalyst precarsor B is obtained；（3）Using reducing atmosphere to step（2）Obtained catalyst precarsor B carries out reduction treatment；（4）By step（3）Catalyst precarsor B after obtained reduction is added to polyhydric alcohol solutions in autoclave, and 2~5h is reacted at 200~300 DEG C；（5）By step（4）Obtained reaction effluent filtering, is dried to obtain catalyst precarsor C；（6）Zinc oxide is introduced to catalyst precarsor C, obtains catalyst precarsor D.（7）Bromination processing is carried out to catalyst precarsor D, it is 0.5% 20% to obtain zinc oxide weight content, zinc bromide weight content for 10% 50% bromomethane preparing isobutene catalyst.Catalyst prepared by this method can improve the selectivity of isobutene.
Description
Technical field
Catalyst the present invention relates to a kind of highly selective preparing isobutene of bromomethane 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, disappears
Take structure in diversified trend.A variety of high value-added products can be prepared by raw material of isobutene, such as：It is butyl rubber, poly- 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, particularly in petroleum resources increasingly depleted
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.Particularly in recent years, under the overall background developed and used in shale gas, 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 profit
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
The further method of reaction generation C3 ~ C13 mixing high-carbon hydrocarbons, the hydrocarbon selective of more than C5 is 70%.Wherein, HBr is at first
It for methane bromination in reactor, is then discharged in second reactor, is used further in back reaction, realizes after recovered
The recycling of HBr.Wang Ye etc.（CN 102527427A, Jieli He, Ting Xu, Zhihui Wang, et.al.
Angew. Chem. Int. Ed. 2012, 51, 2438-2442）Disclose a kind of modified molecules of halide propylene
Sieve catalyst and preparation method thereof.By using fluorochemical moditied processing molecular sieve, obtain one kind and contain appropriate microporous knot
The catalyst of structure and acidity, the catalyst can effectively be catalyzed the reaction that halide is converted into propylene.Prepared catalysis
Agent one way bromomethane conversion ratio in the preparing propylene transformed reaction of bromomethane is 35 ~ 99%, and the selectivity of propylene is 27 ~ 70%；
One way methyl chloride conversion rate is 30 ~ 99% in the preparing propylene transformed reaction of chloromethanes, 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 bromo-hydrocarbons is generated with the alkane reaction in bromine and natural gas,
Then bromo-hydrocarbons is converted into dimethyl ether, methanol and metal bromide, metal bromide oxygen on metal oxide catalyst
Metal oxide is obtained after gas regeneration and releases simple substance bromine, completes the cycle of bromine.
At present, it is mainly methanol, dimethyl ether, acetic acid, high-carbon about purpose product in the existing literature of halide conversion
Hydro carbons, ethylene and propylene etc..Using the low-carbon alkene compared with high added value as in the technology of target product, single selectivity of product
It is not high, not yet find the relevant report of bromomethane high selectivity isobutene.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of catalyst and its system of the highly selective preparing isobutene of bromomethane
Preparation Method.
A kind of preparation method of the catalyst of the highly selective preparing isobutene of bromomethane, including following process：
（1）Ammonium molybdate and ammonium tungstate is soluble in water, obtain solution A；
（2）Carrier is added to step（1）In obtained solution A, after aging, drying, calcination process, catalyst is obtained
Precursor B；In the catalyst precarsor B, the content of molybdenum based on the element in the carrier be 1wt%~8wt%, preferably 3wt%~6wt%,
The content of tungsten based on the element in the carrier is 1wt%~3wt%, and the carrier includes aluminium oxide, silica, Hydrogen ZSM-5 molecules
One or more of sieve, preferably Hydrogen ZSM-5 molecular sieve carrier, further preferred Hydrogen ZSM-5 molecular sieve carrier sial rub
You are than being 20 ~ 200, preferably 20 ~ 150；
（3）Using reducing atmosphere to step（2）Obtained catalyst precarsor B carries out reduction treatment；
（4）By step（3）Catalyst precarsor B after obtained reduction is added to polyhydric alcohol solutions in autoclave,
It is replaced 2~5 times with hydrogen after sealing, then adjusts Hydrogen Vapor Pressure to 2~4MPa, 2~5h is reacted at 200~300 DEG C；
（5）By step（4）Obtained reaction effluent places 1~3h, then filters, obtained solid sample at room temperature into
Row drying, until sample surfaces without liquid phase, obtain catalyst precarsor C；
（6）Zinc oxide is introduced to catalyst precarsor C, obtains catalyst precarsor D.
（7）Bromination processing is carried out to catalyst precarsor D, obtains zinc oxide weight content as 0.5%-20%, zinc bromide weight
Content is the bromomethane preparing isobutene catalyst of 10%-50%.
Above-mentioned preparation method step（1）In, a concentration of 0.05~1mol/L of molybdenum in the solution A, tungsten it is a concentration of
0.01~0.3mol/L.
Above-mentioned preparation method step（2）In, the aging can aging at room temperature, can also be old at a constant temperature
Change, aging temperature is 10~90 DEG C, preferably 20~60 DEG C, ageing time for 1~for 24 hours, preferably 4~12h.The dry temperature
It is 70~150 DEG C, preferably 80~120 DEG C to spend, and drying time is 2~12h, preferably 4~8h.The calcination temperature is 350
~650 DEG C, preferably 400~600 DEG C, roasting time are 2~12h, preferably 4~8h.
Above-mentioned preparation method step（3）In, the reducing atmosphere be hydrogen or the mixed gas of hydrogen and nitrogen, institute
It is 10%~95% to state hydrogen volume percentage composition in gaseous mixture..Specific reduction treatment process is as follows：It will catalysis under nitrogen atmosphere
Agent precursor is warming up to 300~600 DEG C, the mixed gas of hydrogen or hydrogen and nitrogen is then passed to, in 0.1~0.5MPa（Absolute pressure）
After handling 4~8h, it is down to room temperature in a nitrogen atmosphere.
Above-mentioned preparation method step（4）In, the polyalcohol can be xylitol, sorbierite, mannitol, arabite
In it is one or more；The mass concentration of polyhydric alcohol solutions is 5%~10%；Polyhydric alcohol solutions and step（3）After obtained reduction
The volume ratio of catalyst precarsor B is 5~10.
Above-mentioned preparation method step（6）In, the method that the zinc oxide is introduced to catalyst precarsor C is people in the art
Impregnation method introducing such as may be used in method known to member.Specific method is as follows：Using zinc solution impregnation catalyst agent precursor C,
Catalyst precarsor E is obtained after drying, roasting.The drying condition is -150 DEG C of temperature 60 C, preferably 80 DEG C -120 DEG C；
Time is 1h-24h, preferably 4h-8h；Can be vacuum drying when dry, or it is dry under the conditions of inert gas shielding,
It can also dry in air atmosphere.The roasting condition is 200 DEG C -800 DEG C of temperature, preferably 400 DEG C -600 DEG C；Time
For 1h-24h, preferably 4h-8h；It can also can in air atmosphere be roasted to be roasted under the conditions of inert gas shielding during roasting
It burns.In the above method, zinc salt can be inorganic salts, or organic salt, preferably nitrate, hydrochloride, acetate, lemon
One or more of hydrochlorate.
Above-mentioned preparation method step（7）In, the bromination processing refers to using gas phase bromine-containing compound to loading zinc oxide
Sample handled.Bromine-containing compound refers to one or more of bromomethane, methylene bromide, bromoform, preferably bromine
Methane.The mixed gas of gas phase bromine-containing compound and inert gas can also be used to carry out bromination processing, using mixed gas bromine
When changing processing, bromomethane volumetric concentration is not less than 20%, preferably not less than 30%.Specific bromination process is as follows：Oxygen will be loaded
The sample for changing zinc is placed in continuous fixed bed reactor, is warming up to 150 DEG C -400 DEG C under inert atmosphere, 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 velocity 50h-1-1000 h-1, preferably
For 100h-1-500h-1；It can carry out, can also carry out under a certain pressure, system pressure 0.1MPa- in normal pressure during processing
0.5MPa（Absolute pressure）, preferably 0.1MPa-0.3MPa（Absolute pressure）, processing time 0.5h-8h, preferably 1h-4h.
Above-mentioned preparation method step（7）In, involved inert gas is nitrogen, argon gas, helium etc. involved by the present invention
The gas not chemically reacted under the conditions of and, preferably nitrogen.
A kind of catalyst of the highly selective preparing isobutene of bromomethane, based on the weight content of catalyst, zinc oxide content is
0.5%-20%, preferably 1%-15%, further preferably 1%-9%, bromination Zn content be 10%-50%, preferably 15%-45%, into
One step is preferably 18%-39%, further preferably vector contg 40%-90%, preferably 50%-85%, 55%-80%.
In catalyst of the present invention, less than 450 DEG C total acid contents（NH3-TPD）For 0.5mmol/g-1.3mmol/g, preferably
0.6mmol/g-1.2mmol/g, further preferred 0.7mmol-1.1mmol/g, 250 DEG C -350 DEG C of acid content account for 450 DEG C with
The 20%-90% of lower total acid content, preferably 30%-80%, further preferred 40%-80%.
Application of the above-mentioned catalyst in preparing isobutene including carrying out hydrogen reducing activation to catalyst, makes in catalyst
Content of halogen be the 20%-90% for restoring total halogen content in procatalyst, halide and above-mentioned hydrogen reducing is then made to live
Catalyst contact after change, to prepare isobutene.
In above application, the condition of the hydrogen reducing activation causes the content of halogen in catalyst to be urged before preferably restoring
The 30%-80% of total halogen content in agent, further preferred 40%-80%.
In above application, the mode of hydrogen reducing activation include under an inert atmosphere by catalyzer temperature-elevating to 300 DEG C-
600℃；Air speed is then passed to as 200h-1-2000h-1Hydrogen or the mixed gas of hydrogen and inert 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
℃；Air speed is then passed to as 500h-1-1000h-1Hydrogen or the mixed gas of hydrogen and inert gas, in 0.1MPa-
0.3MPa keeps 4h-8h, and hydrogen volume percentage composition is 30%-90% in the mixed gas.
In above application, the halide can be one kind in a halide, methylene halide, three halides
Or it is a variety of, it is preferably one or more in bromomethane, methylene bromide, bromoform.
In above application, it is 150 DEG C -350 DEG C that the condition of the contact, which includes 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。
A kind of specific embodiment in above application, including under inert atmosphere by catalyzer temperature-elevating to 300 DEG C -600 DEG C,
Preferably 350 DEG C -550 DEG C；Air speed is then passed to as 200h-1-2000h-1, preferably 500h-1-1000h-1Hydrogen or hydrogen
With the mixed gas of inert gas, in 0.1MPa-0.5MPa（Absolute pressure）, preferably 0.1MPa-0.3MPa（Absolute pressure）Handle 2h-
After 16h, preferably 4h-8h, it is down to reaction temperature and is passed through halide and reacted.Hydrogen volume percentage contains in the gaseous mixture
It measures as 10%-95%, preferably 30%-90%, more preferably 50%-90%.
In above 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%.
Involved inert gas is not sent out for nitrogen, argon gas, helium etc. under the conditions of involved in the present invention in above application
The gas of biochemical reaction, preferably nitrogen.
In above application, the reaction of halide preparing isobutene can carry out in existing any form reactor, such as fixed
Bed, fluid bed, fixed fluidized bed, moving bed, the preferably reactor of the forms such as slurry bed system or ebullated bed, fixed bed, fluid bed
Reactor.
Compared with prior art, the catalyst for preparing of the present invention can by bromomethane it is highly selective be converted into isobutene.
Bromomethane conversion preparing isobutene reaction, bromomethane conversion ratio are carried out by the method for the present invention85%More than, selective isobutene50%With
On.The present invention relates to bromomethane conversion preparing isobutene method for preparing catalyst it is simple, be easy to industrialize.Bromomethane conversion of the present invention
Preparing isobutene method has many advantages, such as that reaction condition is mild, selectivity of product is high, industrialization easy to implement, and application prospect is very wide
It is wealthy.
Specific embodiment
The technology contents and effect further illustrated the present invention with reference to embodiment, but it is not so limited the present invention.
Acidimetric estimation uses NH in following embodiment and comparative example3- TPD methods, the instrument model used is the U.S.
2920 chemical adsorption instruments of MICROMERITICS companies AutoChem, specific continuous mode are as follows：By sample at 450 DEG C with helium
Purging is cooled to 150 DEG C after 1 hour, introduces the mixed gas of ammonia and helium, ammonia volume content 10%, and Pulse adsorption reaches for five times
Balance；Then helium purge 2 hours carries out ammonia with 10 DEG C/min of heating rate temperature programming and is desorbed to 450 DEG C；After desorption
Ammonia using TCD detectors detect, quantitatively calculate catalyst surface acid amount.
Embodiment 1
It weighs appropriate ammonium molybdate and appropriate ammonium tungstate is dissolved in deionized water, obtain solution A；It is born using equi-volume impregnating
It is loaded in aluminium oxide（Kong Rongwei 0.71ml/g, specific surface area 236m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier, at room temperature always
Change 4h, 80 DEG C of dry 12h, 500 DEG C of roasting 4h are made catalyst precarsor B, wherein Mo and account for vehicle weight 5% based on the element, W is with member
Element meter accounts for vehicle weight 2%；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is in mixed gas
80%, reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；By the catalyst precarsor B and 300mL after reduction activation
The sorbitol solution that mass concentration is 10% is added in autoclave, is replaced 3 times with hydrogen after sealing, is then adjusted hydrogen
Pressure reacts 4h to 3MPa at 220 DEG C；Mixture after being reacted in above-mentioned autoclave is placed into 2h, filtering, obtained solid sample
Product are dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Appropriate zinc nitrate is weighed to be dissolved in deionized water,
Catalyst precarsor C, 80 DEG C of dry 8h are carried on using equi-volume impregnating, 600 DEG C roast 4h, and catalyst precarsor D is made3.It will
5g catalyst precarsors D is placed in continuous fixed bed reactor, handles catalyst precarsor D using bromomethane, treatment conditions are
250 DEG C, 0.2MPa（Absolute pressure）, 100h-1, time 2h is made bromomethane preparing isobutene catalyst, is denoted as C-1.Catalyst weight group
As ZnBr2Weight content is that 30%, ZnO weight contents are 4%, and less than 450 DEG C total acid contents are 0.75mmol/g in catalyst,
250 DEG C -350 DEG C of acid content accounts for the 48.1% of less than 450 DEG C total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading amount 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 50%, and reaction temperature is 230 DEG C, reaction pressure
For 1MPa（Absolute pressure）, air speed 500h-1, it being 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, it is that halogen is total in reduction procatalyst to restore the content of halogen in rear catalyst
The 71.31% of content.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.
Embodiment 2
It weighs appropriate ammonium molybdate and appropriate ammonium tungstate is dissolved in deionized water, obtain solution A；It is born using equi-volume impregnating
It is loaded in silica（Kong Rongwei 1.06ml/g, specific surface area 387m2/ g, spherical, equivalent diameter 0.5mm）Carrier, at room temperature always
Change 8h, 120 DEG C of dry 6h, 600 DEG C of roasting 4h are made catalyst precarsor B, wherein Mo and account for vehicle weight 5% based on the element, W is with member
Element meter accounts for vehicle weight 2%；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is in mixed gas
10%, reducing condition is 500 DEG C, 0.2MPa（Absolute pressure）, recovery time 6h；By the catalyst precarsor B and 300mL after reduction activation
The sorbitol solution that mass concentration is 10% is added in autoclave, is replaced 2 times with hydrogen after sealing, is then adjusted hydrogen
Pressure reacts 4h to 3MPa at 220 DEG C；Mixture after being reacted in above-mentioned autoclave is placed into 3h, filtering, obtained solid sample
Product are dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Appropriate zinc nitrate is weighed to be dissolved in deionized water,
Catalyst precarsor C, 120 DEG C of dry 4h are carried on using equi-volume impregnating, 500 DEG C roast 8h, and catalyst precarsor D is made.It will
5g catalyst precarsors D is placed in continuous fixed bed reactor, and catalyst is handled using the mixed gas of bromomethane and nitrogen
Precursor D, bromomethane volumetric concentration are 80%, and treatment conditions are 250 DEG C, 0.3MPa（Absolute pressure）, 300h-1, time 2h, obtained bromine first
Alkane preparing isobutene catalyst, is denoted as C-2.It is ZnBr to obtain catalyst weight composition2Weight content is counted as 30%, ZnO using bromide
Weight content is counted as 4% using oxide, less than 450 DEG C total acid contents are 0.78mmol/g in catalyst, and 250 DEG C -350 DEG C of acid contains
Amount accounts for the 59.2% of less than 450 DEG C total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading amount 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure
For 2MPa（Absolute pressure）, air speed 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixed gas
Middle hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.3MPa（Absolute pressure）, 800h-1, recovery time 4h is catalyzed after reduction
Content of halogen in agent is restore total halogen content in procatalyst 58.12%.After stable reaction one hour, sampling analysis.Instead
1 should be the results are shown in Table.
Embodiment 3
It weighs appropriate ammonium molybdate and appropriate ammonium tungstate is dissolved in deionized water, obtain solution A；It is born using equi-volume impregnating
It is loaded in Hydrogen ZSM-5（Silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m2/ g, bar shaped, equivalent diameter 1.5mm）It carries
Body, aging 6h, 110 DEG C of dry 10h, 600 DEG C of roasting 4h are made catalyst precarsor B, wherein Mo and account for carrier based on the element at room temperature
Weight 5%, W account for vehicle weight 2% based on the element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Air volume content is 90%, and reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst after reduction activation
Precursor B is added to the sorbitol solution that 300mL mass concentrations are 10% in autoclave, is replaced 4 times with hydrogen after sealing,
Then Hydrogen Vapor Pressure is adjusted to 2MPa, reacts 2h at 300 DEG C；Mixture after being reacted in above-mentioned autoclave is placed into 1h, mistake
Filter, obtained solid sample are dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；It is molten to weigh appropriate zinc nitrate
In deionized water, catalyst precarsor C is carried on using equi-volume impregnating, 100 DEG C of vacuum drying 8h, 400 DEG C roast 8h, system
Obtain catalyst precarsor D.5g catalyst precarsors D is placed in continuous fixed bed reactor, uses the mixed of bromomethane and nitrogen
Gas processing catalyst precursor D is closed, bromomethane volumetric concentration is 30%, and treatment conditions are 300 DEG C, 0.1MPa（Absolute pressure）, 500h-1,
Time 4h is made bromomethane preparing isobutene catalyst, is denoted as C-3.It is ZnBr to obtain catalyst weight composition2It is counted weight with bromide
It is that 30%, ZnO counts weight content as 4% using oxide to measure content, and less than 450 DEG C total acid contents are 0.81mmol/g in catalyst, 250
DEG C -350 DEG C of acid content accounts for the 66.7% of less than 450 DEG C total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading amount 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 80%, and reaction temperature is 200 DEG C, reaction pressure
For 3MPa（Absolute pressure）, air speed 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixed gas
Middle hydrogen volume content is 50%, and reducing condition is 500 DEG C, 0.1MPa（Absolute pressure）, 500h-1, recovery time 4h is catalyzed after reduction
Content of halogen in agent is restore total halogen content in procatalyst 51.37%.After stable reaction one hour, sampling analysis.Instead
1 should be the results are shown in Table.
Embodiment 4
It weighs appropriate ammonium molybdate and appropriate ammonium tungstate is dissolved in deionized water, obtain solution A；It is born using equi-volume impregnating
It is loaded in Hydrogen ZSM-5（Silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m2/ g, bar shaped, equivalent diameter 1.5mm）It carries
Body, aging 6h, 110 DEG C of dry 10h, 600 DEG C of roasting 4h are made catalyst precarsor B, wherein Mo and account for carrier based on the element at room temperature
Weight 5%, W account for vehicle weight 2% based on the element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Air volume content is 90%, and reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst after reduction activation
Precursor B is added to the sorbitol solution that 300mL mass concentrations are 10% in autoclave, is replaced 4 times with hydrogen after sealing,
Then Hydrogen Vapor Pressure is adjusted to 2MPa, reacts 2h at 300 DEG C；Mixture after being reacted in above-mentioned autoclave is placed into 1h, mistake
Filter, obtained solid sample are dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；It is molten to weigh appropriate zinc nitrate
In deionized water, catalyst precarsor C is carried on using equi-volume impregnating, 100 DEG C of vacuum drying 8h, 400 DEG C roast 8h, system
Obtain catalyst precarsor D.5g catalyst precarsors D is placed in continuous fixed bed reactor, uses the mixed of bromomethane and nitrogen
Gas processing catalyst precursor D is closed, bromomethane volumetric concentration is 30%, and treatment conditions are 300 DEG C, 0.1MPa（Absolute pressure）, 500h-1,
Time 4h is made bromomethane preparing isobutene catalyst, is denoted as C-4.It is ZnBr to obtain catalyst weight composition2It is counted weight with bromide
It is that 27%, ZnO counts weight content as 6% using oxide to measure content, and less than 450 DEG C total acid contents are 0.81mmol/g in catalyst, 250
DEG C -350 DEG C of acid content accounts for the 66.7% of less than 450 DEG C total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading amount 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 80%, and reaction temperature is 200 DEG C, reaction pressure
For 3MPa（Absolute pressure）, air speed 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixed gas
Middle hydrogen volume content is 50%, and reducing condition is 500 DEG C, 0.1MPa（Absolute pressure）, 500h-1, recovery time 4h is catalyzed after reduction
Content of halogen in agent is restore total halogen content in procatalyst 51.37%.After stable reaction one hour, sampling analysis.Instead
1 should be the results are shown in Table.
Embodiment 5
It weighs appropriate ammonium molybdate and appropriate ammonium tungstate is dissolved in deionized water, obtain solution A；It is born using equi-volume impregnating
It is loaded in Hydrogen ZSM-5（Silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m2/ g, bar shaped, equivalent diameter 1.5mm）It carries
Body, aging 6h, 110 DEG C of dry 10h, 600 DEG C of roasting 4h are made catalyst precarsor B, wherein Mo and account for carrier based on the element at room temperature
Weight 5%, W account for vehicle weight 2% based on the element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Air volume content is 90%, and reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst after reduction activation
Precursor B is added to the sorbitol solution that 300mL mass concentrations are 10% in autoclave, is replaced 4 times with hydrogen after sealing,
Then Hydrogen Vapor Pressure is adjusted to 2MPa, reacts 2h at 300 DEG C；Mixture after being reacted in above-mentioned autoclave is placed into 1h, mistake
Filter, obtained solid sample are dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；It is molten to weigh appropriate zinc nitrate
In deionized water, catalyst precarsor C is carried on using equi-volume impregnating, 100 DEG C of vacuum drying 8h, 400 DEG C roast 8h, system
Obtain catalyst precarsor D.5g catalyst precarsors D is placed in continuous fixed bed reactor, uses the mixed of bromomethane and nitrogen
Gas processing catalyst precursor D is closed, bromomethane volumetric concentration is 30%, and treatment conditions are 300 DEG C, 0.1MPa（Absolute pressure）, 500h-1,
Time 4h is made bromomethane preparing isobutene catalyst, is denoted as C-5.It is ZnBr to obtain catalyst weight composition2It is counted weight with bromide
It is that 33%, ZnO counts weight content as 2% using oxide to measure content, and less than 450 DEG C total acid contents are 0.81mmol/g in catalyst, 250
DEG C -350 DEG C of acid content accounts for the 66.7% of less than 450 DEG C total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading amount 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 80%, and reaction temperature is 200 DEG C, reaction pressure
For 3MPa（Absolute pressure）, air speed 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixed gas
Middle hydrogen volume content is 50%, and reducing condition is 500 DEG C, 0.1MPa（Absolute pressure）, 500h-1, recovery time 4h is catalyzed after reduction
Content of halogen in agent is restore total halogen content in procatalyst 51.37%.After stable reaction one hour, sampling analysis.Instead
1 should be the results are shown in Table.
Embodiment 6
It weighs appropriate ammonium molybdate and appropriate ammonium tungstate is dissolved in deionized water, obtain solution A；It is born using equi-volume impregnating
It is loaded in Hydrogen ZSM-5（Silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m2/ g, bar shaped, equivalent diameter 1.5mm）It carries
Body, aging 6h, 110 DEG C of dry 10h, 600 DEG C of roasting 4h are made catalyst precarsor B, wherein Mo and account for carrier based on the element at room temperature
Weight 5%, W account for vehicle weight 2% based on the element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Air volume content is 90%, and reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst after reduction activation
Precursor B is added to the arabite solution that 300mL mass concentrations are 10% in autoclave, and 4 are replaced with hydrogen after sealing
It is secondary, Hydrogen Vapor Pressure is then adjusted to 2MPa, reacts 2h at 300 DEG C；Mixture after being reacted in above-mentioned autoclave is placed into 1h,
Filtering, obtained solid sample are dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Weigh appropriate zinc nitrate
It is dissolved in deionized water, catalyst precarsor C, 100 DEG C of vacuum drying 8h, 400 DEG C of roasting 8h is carried on using equi-volume impregnating,
Catalyst precarsor D is made.5g catalyst precarsors D is placed in continuous fixed bed reactor, uses bromomethane and nitrogen
Mixed gas handles catalyst precarsor D, and bromomethane volumetric concentration is 30%, and treatment conditions are 300 DEG C, 0.1MPa（Absolute pressure）,
500h-1, time 4h is made bromomethane preparing isobutene catalyst, is denoted as C-6.It is ZnBr to obtain catalyst weight composition2With bromination
Object meter weight content is that 30%, ZnO counts weight content as 4% using oxide, and less than 450 DEG C total acid contents are in catalyst
0.81mmol/g, 250 DEG C -350 DEG C of acid content account for the 66.7% of less than 450 DEG C total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading amount 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 80%, and reaction temperature is 200 DEG C, reaction pressure
For 3MPa（Absolute pressure）, air speed 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixed gas
Middle hydrogen volume content is 50%, and reducing condition is 500 DEG C, 0.1MPa（Absolute pressure）, 500h-1, recovery time 4h is catalyzed after reduction
Content of halogen in agent is restore total halogen content in procatalyst 51.37%.After stable reaction one hour, sampling analysis.Instead
1 should be the results are shown in Table.
Embodiment 7
It weighs appropriate ammonium molybdate and appropriate ammonium tungstate is dissolved in deionized water, obtain solution A；It is born using equi-volume impregnating
It is loaded in Hydrogen ZSM-5（Silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m2/ g, bar shaped, equivalent diameter 1.5mm）It carries
Body, aging 6h, 110 DEG C of dry 10h, 600 DEG C of roasting 4h are made catalyst precarsor B, wherein Mo and account for carrier based on the element at room temperature
Weight 5%, W account for vehicle weight 2% based on the element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Air volume content is 90%, and reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst after reduction activation
The sorbitol solution that precursor B and 300mL mass concentrations are 5% is added in autoclave, replaces 4 times with hydrogen after sealing, so
Hydrogen Vapor Pressure is adjusted afterwards to 2MPa, reacts 2h at 300 DEG C；Mixture after being reacted in above-mentioned autoclave is placed into 1h, is filtered,
Obtained solid sample is dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Appropriate zinc nitrate is weighed to be dissolved in
In ionized water, catalyst precarsor C is carried on using equi-volume impregnating, 100 DEG C of vacuum drying 8h, 400 DEG C roast 8h, are made and urge
Agent precursor D.5g catalyst precarsors D is placed in continuous fixed bed reactor, uses bromomethane and the gaseous mixture of nitrogen
Body handles catalyst precarsor D, and bromomethane volumetric concentration is 30%, and treatment conditions are 300 DEG C, 0.1MPa（Absolute pressure）, 500h-1, the time
4h is made bromomethane preparing isobutene catalyst, is denoted as C-7.It is ZnBr to obtain catalyst weight composition2Contained with bromide weight calculation amount
It measures and weight content is counted as 4% using oxide for 30%, ZnO, less than 450 DEG C total acid contents are 0.81mmol/g in catalyst, 250 DEG C-
350 DEG C of acid content accounts for the 66.7% of less than 450 DEG C total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading amount 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 80%, and reaction temperature is 200 DEG C, reaction pressure
For 3MPa（Absolute pressure）, air speed 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixed gas
Middle hydrogen volume content is 50%, and reducing condition is 500 DEG C, 0.1MPa（Absolute pressure）, 500h-1, recovery time 4h is catalyzed after reduction
Content of halogen in agent is restore total halogen content in procatalyst 51.37%.After stable reaction one hour, sampling analysis.Instead
1 should be the results are shown in Table.
Comparative example 1
It weighs appropriate ammonium molybdate and appropriate ammonium tungstate is dissolved in deionized water, obtain solution A；It is born using equi-volume impregnating
It is loaded in Hydrogen ZSM-5（Silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m2/ g, bar shaped, equivalent diameter 1.5mm）It carries
Body, aging 6h, 110 DEG C of dry 10h, 600 DEG C of roasting 4h are made catalyst precarsor B, wherein Mo and account for carrier based on the element at room temperature
Weight 5%, W account for vehicle weight 2% based on the element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Air volume content is 90%, and reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst after reduction activation
Precursor B is added to the sorbitol solution that 300mL mass concentrations are 10% in autoclave, is replaced 4 times with hydrogen after sealing,
Then Hydrogen Vapor Pressure is adjusted to 2MPa, reacts 2h at 300 DEG C；Mixture after being reacted in above-mentioned autoclave is placed into 1h, mistake
Filter, obtained solid sample are dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；It is molten to weigh appropriate zinc nitrate
In deionized water, catalyst precarsor C is carried on using equi-volume impregnating, 100 DEG C of vacuum drying 8h, 400 DEG C roast 8h, system
Catalyst is obtained, is denoted as D-1.
It is 20% to obtain catalyst weight to form being ZnO weight contents in terms of oxide, less than 450 DEG C total acids in catalyst
It measures as 0.38mmol/g, 250 DEG C -350 DEG C of acid content accounts for the 35.5% of less than 450 DEG C total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading amount 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 80%, and reaction temperature is 200 DEG C, reaction pressure
For 3MPa（Absolute pressure）, air speed 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixed gas
Middle hydrogen volume content is 50%, and reducing condition is 500 DEG C, 0.1MPa（Absolute pressure）, 500h-1, recovery time 4h.Stable reaction one
After hour, sampling analysis.Reaction result is shown in Table 1.
Comparative example 2
It weighs appropriate ammonium molybdate and appropriate ammonium tungstate is dissolved in deionized water, obtain solution A；It is born using equi-volume impregnating
It is loaded in Hydrogen ZSM-5（Silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m2/ g, bar shaped, equivalent diameter 1.5mm）It carries
Body, aging 6h, 110 DEG C of dry 10h, 600 DEG C of roasting 4h are made catalyst precarsor B, wherein Mo and account for carrier based on the element at room temperature
Weight 5%, W account for vehicle weight 2% based on the element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Air volume content is 90%, and reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst after reduction activation
Precursor B is added to the sorbitol solution that 300mL mass concentrations are 10% in autoclave, is replaced 4 times with hydrogen after sealing,
Then Hydrogen Vapor Pressure is adjusted to 2MPa, reacts 2h at 300 DEG C；Mixture after being reacted in above-mentioned autoclave is placed into 1h, mistake
Filter, obtained solid sample are dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；It is molten to weigh appropriate zinc nitrate
In deionized water, catalyst precarsor C is carried on using equi-volume impregnating, 100 DEG C of vacuum drying 8h, 400 DEG C roast 8h, system
Obtain catalyst precarsor D.5g catalyst precarsors D is placed in continuous fixed bed reactor, uses the mixed of bromomethane and nitrogen
Gas processing catalyst precursor D is closed, bromomethane volumetric concentration is 30%, and treatment conditions are 300 DEG C, 0.1MPa（Absolute pressure）, 500h-1,
Time 4h is made bromomethane preparing isobutene catalyst, is denoted as D-2.It is ZnBr to obtain catalyst weight composition2It is counted weight with bromide
It is that 30%, ZnO counts weight content as 4% using oxide to measure content, and less than 450 DEG C total acid contents are 0.81mmol/g in catalyst, 250
DEG C -350 DEG C of acid content accounts for the 66.7% of less than 450 DEG C total acid contents.
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading amount 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 80%, and reaction temperature is 200 DEG C, reaction pressure
For 3MPa（Absolute pressure）, air speed 350h-1.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.
Comparative example 3
It weighs appropriate ammonium molybdate and appropriate ammonium tungstate is dissolved in deionized water, obtain solution A；It is born using equi-volume impregnating
It is loaded in Hydrogen ZSM-5（Silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m2/ g, bar shaped, equivalent diameter 1.5mm）It carries
Body, aging 6h, 110 DEG C of dry 10h, 600 DEG C of roasting 4h are made catalyst precarsor B, wherein Mo and account for carrier based on the element at room temperature
Weight 5%, W account for vehicle weight 2% based on the element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Air volume content is 90%, and reducing condition is 400 DEG C, 0.2MPa（Absolute pressure）, recovery time 8h；By the catalyst after reduction activation
Precursor B is added to the sorbitol solution that 300mL mass concentrations are 10% in autoclave, is replaced 4 times with hydrogen after sealing,
Then Hydrogen Vapor Pressure is adjusted to 2MPa, reacts 2h at 300 DEG C；Mixture after being reacted in above-mentioned autoclave is placed into 1h, mistake
Filter, obtained solid sample are dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；It is molten to weigh appropriate zinc bromide
In deionized water, catalyst precarsor C is carried on using equi-volume impregnating, 80 DEG C of nitrogen atmospheres dry 4h, 500 DEG C of nitrogen gas
Atmosphere roasts 4h, and catalyst is made, is denoted as D-3.It is ZnBr to obtain catalyst weight composition2Weight content is counted as 30% using bromide,
Less than 450 DEG C total acid contents are 0.95mmol/g in catalyst, and 250 DEG C -350 DEG C of acid content accounts for less than 450 DEG C total acid contents
70.3%。
Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading amount 5g,
Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 80%, and reaction temperature is 200 DEG C, reaction pressure
For 3MPa（Absolute pressure）, air speed 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixed gas
Middle hydrogen volume content is 50%, and reducing condition is 500 DEG C, 0.1MPa（Absolute pressure）, 500h-1, recovery time 4h is catalyzed after reduction
Content of halogen in agent is restore total halogen content in procatalyst 51.37%.After stable reaction one hour, sampling analysis.Instead
1 should be the results are shown in Table.
1 catalyst reaction performance of table
Claims (23)
1. a kind of preparation method of the catalyst of the highly selective preparing isobutene of bromomethane, it is characterised in that：Including following process：
（1）Ammonium molybdate and ammonium tungstate is soluble in water, obtain solution A；
（2）Carrier is added to step（1）In obtained solution A, after aging, drying, calcination process, catalyst precarsor is obtained
B；In the catalyst precarsor B, the content of molybdenum based on the element in the carrier is 1wt%~8wt%, and tungsten is based on the element in the carrier
Content is 1wt%~3wt%, and the carrier is selected from one or more of aluminium oxide, silica, Hydrogen ZSM-5 molecular sieve；
（3）Using reducing atmosphere to step（2）Obtained catalyst precarsor B carries out reduction treatment；
（4）By step（3）Catalyst precarsor B after obtained reduction is added to polyhydric alcohol solutions in autoclave, is sealed
It is replaced 2~5 times with hydrogen afterwards, then adjusts Hydrogen Vapor Pressure to 2~4MPa, 2~5h is reacted at 200~300 DEG C；
（5）By step（4）Obtained reaction effluent places 1~3h, then filters, obtained solid sample is done at room temperature
It is dry, until sample surfaces without liquid phase, obtain catalyst precarsor C；
（6）Zinc oxide is introduced to catalyst precarsor C, obtains catalyst precarsor D；
（7）Bromination processing is carried out to catalyst precarsor D, obtains zinc oxide weight content as 0.5%-20%, zinc bromide weight content
Bromomethane preparing isobutene catalyst for 10%-50%.
2. according to the method described in claim 1, it is characterized in that：Step（1）A concentration of 0.05~1mol/ of molybdenum in solution A
L, a concentration of 0.01~0.3mol/L of tungsten.
3. according to the method described in claim 1, it is characterized in that：Step（2）Middle aging temperature is 10~90 DEG C, ageing time
For 1~for 24 hours, drying temperature is 70~150 DEG C, and drying time is 2~12h, and calcination temperature is 350~650 DEG C, and roasting time is
2~12h.
4. according to the method described in claim 1, it is characterized in that：Step（2）Middle carrier is Hydrogen ZSM-5 molecular sieve carrier,
The silica alumina ratio of molecular sieve is 20 ~ 200.
5. according to the method described in claim 1, it is characterized in that：Step（3）Described in reducing atmosphere be hydrogen or hydrogen
The mixed gas of gas and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.
6. according to the method described in claim 5, it is characterized in that：Specific reduction treatment process is as follows：It will under nitrogen atmosphere
Catalyst precarsor B is warming up to 300~600 DEG C, the mixed gas of hydrogen or hydrogen and nitrogen is then passed to, in 0.1~0.5MPa
After handling 4~8h, it is down to room temperature in a nitrogen atmosphere, wherein, pressure is in terms of absolute pressure.
7. according to the method described in claim 1, it is characterized in that：Step（4）Described in polyalcohol be selected from xylitol, sorb
It is one or more in alcohol, mannitol, arabite；The mass concentration of polyhydric alcohol solutions is 5%~10%；Polyhydric alcohol solutions and step
Suddenly（3）The volume ratio of catalyst precarsor B after obtained reduction is 5~10.
8. according to the method described in claim 1, it is characterized in that：Step（6）Middle zinc oxide is introduced to catalyst precarsor C uses
Impregnation method introduces.
9. according to the method described in claim 8, it is characterized in that：Using zinc solution impregnation catalyst agent precursor C, through drying,
Catalyst precarsor D is obtained after roasting, drying temperature is 60 DEG C -150 DEG C, time 1h-24h, 200 DEG C -800 DEG C of calcination temperature,
Time is 1h-24h.
10. according to the method described in claim 9, it is characterized in that：Zinc salt is nitrate, hydrochloride, acetate, citrate
One or more of.
11. according to the method described in claim 1, it is characterized in that：Step（7）Described in bromination processing refer to contain using gas phase
Bromine compounds is to catalyst precarsor D processing.
12. according to the method for claim 11, it is characterised in that：Bromine-containing compound refers to bromomethane, methylene bromide, tribromo
One or more of methane.
13. according to the method for claim 12, it is characterised in that：Using the mixing of gas phase bromine-containing compound and inert gas
Gas carries out bromination processing, and bromomethane volumetric concentration is not less than 20%.
14. according to the method for claim 11, it is characterised in that：Specific bromination process is as follows：Catalyst precarsor D is placed in
In continuous fixed bed reactor, 150 DEG C -400 DEG C are warming up under inert atmosphere, is passed through gas phase bromine-containing compound gas, gas
Body air speed is 50h-1-1000 h-1；System pressure is 0.1MPa-0.5MPa, wherein, in terms of absolute pressure, processing time is pressure
0.5h-8h。
15. according to the method for claim 14, it is characterised in that：180 DEG C -350 DEG C are warming up under inert atmosphere, is passed through gas
Phase bromine-containing compound gas, gas space velocity 100h-1-500h-1；System pressure is 0.1MPa-0.3MPa, wherein, pressure is with exhausted
Pressure meter, processing time 1h-4h.
16. a kind of catalyst prepared using claim 1 to 15 either method, it is characterised in that：Contain by the weight of catalyst
Gauge, zinc oxide content 0.5%-20%, bromination Zn content are 10%-50%, vector contg 40%-85%.
17. catalyst according to claim 16, it is characterised in that：Less than 450 DEG C total acid contents are 0.5mmol/g-
1.3mmol/g, 250 DEG C -350 DEG C of acid content account for the 20%-90% of less than 450 DEG C total acid contents.
18. application of the catalyst described in claim 16 in preparing isobutene, it is characterised in that：Including carrying out hydrogen to catalyst
Reduction activation, it is the 20%-90% for restoring total halogen content in procatalyst to make the content of halogen in catalyst, then makes bromomethane
Catalyst after being activated with hydrogen reducing contacts, to prepare isobutene.
19. application according to claim 18, it is characterised in that：The condition of the hydrogen reducing activation causes in catalyst
Content of halogen be restore procatalyst in total halogen content 30%-80%.
20. application according to claim 18, 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；Air speed is then passed to as 200h-1-2000h-1Hydrogen or hydrogen and indifferent gas
The mixed gas of body keeps 2h-16h in 0.1MPa-0.5MPa, wherein, pressure is in terms of absolute pressure, hydrogen volume hundred in mixed gas
It is 10%-95% to divide content.
21. application according to claim 18, it is characterised in that：The condition of the contact include reaction temperature for 150 DEG C-
350℃；Reaction pressure is 0.1MPa-5MPa, wherein, pressure is in terms of absolute pressure, air speed 50h-1-1000h-1。
22. application according to claim 18, it is characterised in that：Mixed gas of the raw material for bromomethane and inert gas,
The volumetric concentration of bromomethane is 10%-90% in mixed gas.
23. application according to claim 18, it is characterised in that：Bromomethane preparing isobutene reaction fixed bed, fluid bed,
It is carried out in moving bed or paste state bed reactor.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026944A (en) * | 1989-12-20 | 1991-06-25 | Energy Mines And Resources Canada | Synthesis of isobutene from methane and acetylene |
| EP1227074A1 (en) * | 2001-01-29 | 2002-07-31 | Takefumi Hatanaka | Method and system for producing heavier hydrocarbons from solid carbon and water |
| CN103420750A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing olefin from low-carbon alkane |
| CN103506158A (en) * | 2013-10-25 | 2014-01-15 | 凯瑞化工股份有限公司 | Catalyst applicable to reaction in production of isobutene through tertiary butanol dehydration and preparation method thereof |
| CN104292066A (en) * | 2014-09-04 | 2015-01-21 | 深圳市飞扬实业有限公司 | Preparation method for high purity isobutylene |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026944A (en) * | 1989-12-20 | 1991-06-25 | Energy Mines And Resources Canada | Synthesis of isobutene from methane and acetylene |
| EP1227074A1 (en) * | 2001-01-29 | 2002-07-31 | Takefumi Hatanaka | Method and system for producing heavier hydrocarbons from solid carbon and water |
| CN103420750A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing olefin from low-carbon alkane |
| CN103506158A (en) * | 2013-10-25 | 2014-01-15 | 凯瑞化工股份有限公司 | Catalyst applicable to reaction in production of isobutene through tertiary butanol dehydration and preparation method thereof |
| CN104292066A (en) * | 2014-09-04 | 2015-01-21 | 深圳市飞扬实业有限公司 | Preparation method for high purity isobutylene |
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