CN106140223B - A kind of bromomethane preparing isobutene catalyst and its preparation method and application - Google Patents
A kind of bromomethane preparing isobutene catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of bromomethane preparing isobutene catalyst and its preparation method and application.The preparation method of catalyst, comprises the following processes: (1) zinc oxide/or auxiliary agent oxide zirconium being introduced to silica supports, then high-temperature roasting is handled；(2) remaining zinc oxide is introduced to step (1) resulting silica supports, then low-temperature bake is handled；(3) bromination processing is carried out to the carrier after introducing zinc oxide, bromination to zinc oxide weight content is 0.5%-20%, and zinc bromide weight content is 10%-50%.The catalyst is capable of providing the selectivity of isobutene.
Description
Technical field
The present invention relates to a kind of bromomethane preparing isobutene catalyst and its preparation method and application, relate in particular to one kind
Using improved silica as highly selective preparing isobutene catalyst of the bromomethane of carrier and its preparation method and application.
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.
One 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 that reaction generates C3 ~ C13 mixing high-carbon hydrocarbon, the hydrocarbon selective of C5 or more are 70%.Wherein, HBr is at first
It is used for methane bromination in reactor, is then discharged in second reactor, is used further in back reaction, realizes after recovered
The recycling of HBr.(CN 102527427A, Jieli He, Ting Xu, the Zhihui Wang, et.al. such as Wang Ye
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, obtains 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 dimethyl ether, methanol and metal bromide, metal bromide oxygen are converted by bromo-hydrocarbons on metal oxide catalyst
Metal oxide is obtained after gas regeneration and 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 using improved silica as the bromomethane high selection of carrier
Property generate isobutene catalyst and its preparation method and application.
A kind of preparation method of bromomethane preparing isobutene catalyst, comprises the following processes: (1) by zinc oxide/or auxiliary agent oxygen
Compound zirconium is introduced to silica supports, and then high-temperature roasting is handled；(2) that remaining zinc oxide is introduced to step (1) is resulting
Silica supports, then low-temperature bake is handled；(3) bromination processing, bromination to oxidation are carried out to the carrier after introducing zinc oxide
Zinc weight content is 0.5%-20%, and zinc bromide weight content is 10%-50%.
In the preparation method of above-mentioned bromomethane preparing isobutene catalyst, step (1) described silica supports can be used
Existing silica product can also be prepared by method well known to those skilled in the art.Carrier can be according to the needs of use
It is made or is chosen suitable particle shape, such as bar shaped, piece shape, cylindricality, spherical shape is made.Forming can be by this field general knowledge
It carries out.
Zinc oxide and/or auxiliary agent zirconium oxide described in the preparation method step (1) of above-mentioned bromomethane preparing isobutene catalyst
The method for being introduced to silica supports is method well known to those skilled in the art, can such as be introduced using impregnation method.Tool
Body method is as follows: using zinc salt, promoter metal zirconium salt solution impregnated carrier, then dry, high-temperature roasting.The drying condition
For, under air atmosphere, -150 DEG C of temperature 60 C, preferably 80 DEG C -120 DEG C；Time is 1h-24h, preferably 4h-8h.The roasting
Burning condition is, under air atmosphere, 600 DEG C -1000 DEG C of temperature, preferably 700 DEG C -900 DEG C；Time is 1h-24h, preferably 4h-
8h.The zinc oxide amount of introducing described in step (1) accounts for the 1%-20%, preferably 5%- of total zinc of catalyst introducing in mol
15%。
Zinc oxide described in the preparation method step (2) of above-mentioned bromomethane preparing isobutene catalyst is introduced to silica load
The method of body is method well known to those skilled in the art, can such as be introduced using impregnation method.The specific method is as follows: using zinc
The material that salt solution impregnation step (1) obtains obtains bromomethane preparing isobutene catalyst precarsor after drying, roasting.It is described dry
Dry condition is -150 DEG C of temperature 60 C, preferably 80 DEG C -120 DEG C；Time is 1h-24h, preferably 4h-8h；It can be with when dry
For vacuum drying, or it is dry under the conditions of inert gas shielding, it can also dry in air atmosphere.The roasting condition
For 300 DEG C -600 DEG C of temperature, preferably 400 DEG C -500 DEG C；Time is 1h-24h, preferably 4h-8h；It can be lazy when roasting
It roasts, can also be roasted under the conditions of property gas shield in air atmosphere.
In above method step (1) and step (2), zinc salt can be inorganic salts, or organic salt, preferably nitric acid
One or more of salt, hydrochloride, acetate, 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 zinc 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 zinc 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.
A kind of bromomethane preparing isobutene catalyst, containing zinc oxide, zinc bromide and silica supports, zinc oxide weight contains
Amount is 0.5%-20%, preferably 1%-15%, further preferred 1%-9%；Zinc bromide weight content be 10%-50%, preferably 15%-45%,
Further preferred 18%-39%；Silica supports weight content 40%-90%, preferably 50%-85%, further preferred 55%-80%.
In above-mentioned bromomethane preparing isobutene catalyst, suitable auxiliary agent zirconium can also be contained, zirconium is based on the element in catalyst
In weight content be 0.1%-10%, preferably 0.5%-5%, more preferably 0.5%-3%.
In above-mentioned bromomethane preparing isobutene catalyst, 450 DEG C or less total acid contents (NH3-TPD) are 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
Acid content accounts for the 20%-90% of 450 DEG C or less total acid contents, preferably 30%-80%, further preferred 40%-80%.
The above-mentioned application using improved silica as the catalyst of carrier in preparing isobutene, including hydrogen is carried out to catalyst
Gas reduction activation makes the content of halogen in catalyst restore the 20%-90% of total halogen content in procatalyst, then makes halogenated
Catalyst after methane is activated with above-mentioned hydrogen reducing contacts, 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.?
In the present invention, a part of zinc oxide is preferentially impregnated, forms strong interaction species through high-temperature roasting and silica, it can be more preferable
Realization Electron Transfer.By the method for the present invention carry out bromomethane conversion preparing isobutene reaction, bromomethane conversion ratio 80% with
On, 70% or more selective isobutene.The present invention relates to bromomethane conversion preparing isobutene method for preparing catalyst it is simple, be easy to work
Industry.Bromomethane conversion preparing isobutene method of the present invention has many advantages, such as that reaction condition is mild, selectivity of product is high, easy to accomplish
Industrialization, 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.
Acidimetric estimation uses NH in following embodiment and comparative example3- TPD method, the instrument model used is the U.S.
2920 chemical adsorption instrument of MICROMERITICS company AutoChem, specific continuous mode are as follows: by sample at 450 DEG C with helium
Purging was cooled to 150 DEG C after 1 hour, introduced the mixed gas of ammonia and helium, ammonia volume content 10%, reached for Pulse adsorption five times
Balance；Helium purge 2 hours, ammonia is then carried out with 10 DEG C/min of heating rate temperature programming and is desorbed to 450 DEG C；After desorption
Ammonia using TCD detector detect, quantitatively calculate catalyst surface acid amount.
Embodiment 1
It weighs appropriate zinc nitrate to be dissolved in deionized water, silica supports (Kong Rong is carried on using equi-volume impregnating
For 1.06ml/g, specific surface area 387m2/ g, spherical, equivalent diameter 0.5mm), 100 DEG C of dry 6h, 800 DEG C of roasting 6h, system contain
The silica supports of zinc oxide, wherein zinc oxide introduction volume accounts for 10% that catalyst always introduces zinc in mol.It weighs again appropriate
Zinc nitrate is dissolved in deionized water, is carried on the silica supports containing zinc oxide, 100 DEG C of dryings using equi-volume impregnating
Catalyst precarsor ZnO/SiO is made in 6h, 450 DEG C of roasting 6h2.Catalyst precarsor is placed in continuous fixed bed reactor,
Catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 80%, 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-1.Obtain catalyst weight composition
For ZnBr2It is 4% that weight content, which is 30%, ZnO weight content in terms of oxide, in terms of bromide, in catalyst 450 DEG C or less it is total
Acid amount is 0.88mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 76.51% of 450 DEG C or less total acid contents.
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 65.30% 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
It weighs appropriate zinc nitrate to be dissolved in deionized water, silica supports (Kong Rong is carried on using equi-volume impregnating
For 1.06ml/g, specific surface area 387m2/ g, spherical, equivalent diameter 0.5mm), 100 DEG C of dry 6h, 800 DEG C of roasting 6h, system contain
The silica supports of zinc oxide, wherein zinc oxide introduction volume accounts for 5% that catalyst always introduces zinc in mol.It weighs again appropriate
Zinc nitrate is dissolved in deionized water, is carried on the silica supports containing zinc oxide, 100 DEG C of dryings using equi-volume impregnating
Catalyst precarsor ZnO/SiO is made in 6h, 450 DEG C of roasting 6h2.Catalyst precarsor is placed in continuous fixed bed reactor,
Catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 80%, 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-2.Obtain catalyst weight composition
For ZnBr2It is 4% that weight content, which is 30%, ZnO weight content in terms of oxide, in terms of bromide, in catalyst 450 DEG C or less it is total
Acid amount is 0.91mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 74.53% of 450 DEG C or less total acid contents.
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 57.31% 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
It weighs appropriate zinc nitrate to be dissolved in deionized water, silica supports (Kong Rong is carried on using equi-volume impregnating
For 1.06ml/g, specific surface area 387m2/ g, spherical, equivalent diameter 0.5mm), 100 DEG C of dry 6h, 800 DEG C of roasting 6h, system contain
The silica supports of zinc oxide, wherein zinc oxide introduction volume accounts for 15% that catalyst always introduces zinc in mol.It weighs again appropriate
Zinc nitrate is dissolved in deionized water, is carried on the silica supports containing zinc oxide, 100 DEG C of dryings using equi-volume impregnating
Catalyst precarsor ZnO/SiO is made in 6h, 450 DEG C of roasting 6h2.Catalyst precarsor is placed in continuous fixed bed reactor,
Catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 80%, 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 weight composition
For ZnBr2It is 4% that weight content, which is 30%, ZnO weight content in terms of oxide, in terms of bromide, in catalyst 450 DEG C or less it is total
Acid amount is 0.83mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 79.92% of 450 DEG C or less total acid contents.
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 62.17% 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 4
It weighs appropriate zinc nitrate to be dissolved in deionized water, silica supports (Kong Rong is carried on using equi-volume impregnating
For 1.06ml/g, specific surface area 387m2/ g, spherical, equivalent diameter 0.5mm), 100 DEG C of dry 6h, 800 DEG C of roasting 6h, system contain
The silica supports of zinc oxide, wherein zinc oxide introduction volume accounts for 10% that catalyst always introduces zinc in mol.It weighs again appropriate
Zinc nitrate is dissolved in deionized water, is carried on the silica supports containing zinc oxide, 100 DEG C of dryings using equi-volume impregnating
Catalyst precarsor ZnO/SiO is made in 6h, 450 DEG C of roasting 6h2.Catalyst precarsor is placed in continuous fixed bed reactor,
Catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 80%, 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-4.Obtain catalyst weight composition
For ZnBr2It is 2% that weight content, which is 18%, ZnO weight content in terms of oxide, in terms of bromide, in catalyst 450 DEG C or less it is total
Acid amount is 0.73mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 75.42% of 450 DEG C or less total acid contents.
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 59.27% 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 5
It weighs appropriate zinc nitrate to be dissolved in deionized water, silica supports (Kong Rong is carried on using equi-volume impregnating
For 1.06ml/g, specific surface area 387m2/ g, spherical, equivalent diameter 0.5mm), 100 DEG C of dry 6h, 800 DEG C of roasting 6h, system contain
The silica supports of zinc oxide, wherein zinc oxide introduction volume accounts for 10% that catalyst always introduces zinc in mol.It weighs again appropriate
Zinc nitrate is dissolved in deionized water, is carried on the silica supports containing zinc oxide, 100 DEG C of dryings using equi-volume impregnating
Catalyst precarsor ZnO/SiO is made in 6h, 450 DEG C of roasting 6h2.Catalyst precarsor is placed in continuous fixed bed reactor,
Catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 80%, 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-5.Obtain catalyst weight composition
For ZnBr2It is 6% that weight content, which is 39%, ZnO weight content in terms of oxide, in terms of bromide, in catalyst 450 DEG C or less it is total
Acid amount is 0.95mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 76.77% of 450 DEG C or less total acid contents.
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 63.48% 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 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed 200h-1.Reaction is steady
After one hour fixed, sampling analysis.Reaction result is shown in Table 1.
Embodiment 6
It weighs appropriate zinc nitrate to be dissolved in deionized water, silica supports (Kong Rong is carried on using equi-volume impregnating
For 1.06ml/g, specific surface area 387m2/ g, spherical, equivalent diameter 0.5mm), 80 DEG C of dry 8h, 900 DEG C of roasting 4h, system contain
The silica supports of zinc oxide, wherein zinc oxide introduction volume accounts for 10% that catalyst always introduces zinc in mol.It weighs again appropriate
Zinc nitrate is dissolved in deionized water, is carried on the silica supports containing zinc oxide using equi-volume impregnating, 80 DEG C of dry 8h,
Catalyst precarsor ZnO/SiO is made in 500 DEG C of roasting 4h2.Catalyst precarsor is placed in continuous fixed bed reactor, is made
Catalyst precarsor is handled with the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 80%, 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-6.Obtain catalyst weight composition
For ZnBr2It is 4% that weight content, which is 30%, ZnO weight content in terms of oxide, in terms of bromide, in catalyst 450 DEG C or less it is total
Acid amount is 0.86mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 73.28% of 450 DEG C or less total acid contents.
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 4h；Restoring the content of halogen in rear catalyst is reduction procatalyst
The 55.69% 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 3MPa(absolute pressure), air speed 500h-1.Stable reaction
After one hour, sampling analysis.Reaction result is shown in Table 1.
Embodiment 7
It weighs appropriate zinc nitrate to be dissolved in deionized water, silica supports (Kong Rong is carried on using equi-volume impregnating
For 1.06ml/g, specific surface area 387m2/ g, spherical, equivalent diameter 0.5mm), 120 DEG C of dry 4h, 700 DEG C of roasting 8h, system contain
The silica supports of zinc oxide, wherein zinc oxide introduction volume accounts for 10% that catalyst always introduces zinc in mol.It weighs again appropriate
Zinc nitrate is dissolved in deionized water, is carried on the silica supports containing zinc oxide, 120 DEG C of dryings using equi-volume impregnating
Catalyst precarsor ZnO/SiO is made in 4h, 400 DEG C of roasting 8h2.Catalyst precarsor is placed in continuous fixed bed reactor,
Catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 80%, 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-7.Obtain catalyst weight composition
For ZnBr2It is 4% that weight content, which is 30%, ZnO weight content in terms of oxide, in terms of bromide, in catalyst 450 DEG C or less it is total
Acid amount is 0.85mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 72.99% of 450 DEG C or less total acid contents.
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 54.12% 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 0.1MPa(absolute pressure), air speed 350h-1.Reaction is steady
After one hour fixed, sampling analysis.Reaction result is shown in Table 1.
Embodiment 8
It weighs appropriate zinc nitrate to be dissolved in deionized water, silica supports (Kong Rong is carried on using equi-volume impregnating
For 1.06ml/g, specific surface area 387m2/ g, spherical, equivalent diameter 0.5mm), 100 DEG C of dry 6h, 800 DEG C of roasting 6h, system contain
The silica supports of zinc oxide, wherein zinc oxide introduction volume accounts for 10% that catalyst always introduces zinc in mol.It weighs again appropriate
Zinc nitrate is dissolved in deionized water, is carried on the silica supports containing zinc oxide, 100 DEG C of dryings using equi-volume impregnating
Catalyst precarsor ZnO/SiO is made in 6h, 450 DEG C of roasting 6h2.Catalyst precarsor is placed in continuous fixed bed reactor,
Catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 30%, and treatment conditions are 300 DEG C,
0.3MPa(absolute pressure), 100h-1, time 4h, be made bromomethane preparing isobutene catalyst, be denoted as C-8.Obtain catalyst weight composition
For ZnBr2It is 4% that weight content, which is 30%, ZnO weight content in terms of oxide, in terms of bromide, in catalyst 450 DEG C or less it is total
Acid amount is 0.79mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 75.46% of 450 DEG C or less total acid contents.
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 60.54% 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 9
It weighs appropriate zinc nitrate to be dissolved in deionized water, silica supports (Kong Rong is carried on using equi-volume impregnating
For 1.06ml/g, specific surface area 387m2/ g, spherical, equivalent diameter 0.5mm), 100 DEG C of dry 6h, 800 DEG C of roasting 6h, system contain
The silica supports of zinc oxide, wherein zinc oxide introduction volume accounts for 10% that catalyst always introduces zinc in mol.It weighs again appropriate
Zinc nitrate is dissolved in deionized water, is carried on the silica supports containing zinc oxide, 100 DEG C of dryings using equi-volume impregnating
Catalyst precarsor ZnO/SiO is made in 6h, 450 DEG C of roasting 6h2.Catalyst precarsor is placed in continuous fixed bed reactor,
Catalyst precarsor is handled using bromomethane, treatment conditions are 200 DEG C, 0.1MPa(absolute pressure), 500h-1, time 1h, obtained bromomethane
Preparing isobutene catalyst, is denoted as C-9.Catalyst weight group is obtained as ZnBr2In terms of bromide weight content be 30%, ZnO with
Oxide meter weight content is 4%, and 450 DEG C or less total acid contents are 0.91mmol/g, 250 DEG C -350 DEG C of acid content in catalyst
Account for the 75.7% of 450 DEG C or less total acid contents.
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 59.81% 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 10
Weigh appropriate zinc nitrate, zirconium nitrate is dissolved in deionized water, using equi-volume impregnating be carried on silica carry
Body (Kong Rongwei 1.06ml/g, specific surface area 387m2/ g, spherical, equivalent diameter 0.5mm), 100 DEG C of dry 6h, 800 DEG C of roastings
6h makes the silica supports containing zinc oxide, and wherein zinc oxide introduction volume accounts for 10% that catalyst always introduces zinc in mol.Again
It weighs appropriate zinc nitrate to be dissolved in deionized water, the silica supports containing zinc oxide is carried on using equi-volume impregnating, 100
DEG C dry 6h, 450 DEG C of roasting 6h, obtained catalyst precarsor ZnO/SiO2.It is anti-that catalyst precarsor is placed in continuous flow fixed bed
It answers in device, handles catalyst precarsor using the mixed gas of bromomethane and nitrogen, bromomethane volumetric concentration is 80%, treatment conditions
It is 250 DEG C, 0.2MPa(absolute pressure), 300h-1, time 2h, be made bromomethane preparing isobutene catalyst, be denoted as C-10.It is catalyzed
Agent weight group becomes ZnBr2It is 4% that weight content, which is 30%, ZnO weight content in terms of oxide, in terms of bromide, and zirconium is based on the element
Weight content is 2%, and 450 DEG C or less total acid contents are 0.9mmol/g in catalyst, 250 DEG C -350 DEG C of acid content account for 450 DEG C with
The 76.17% of lower total acid content.
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 58.90% 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.Detailed process is as follows:
It weighs appropriate zinc nitrate to be dissolved in deionized water, silica supports (Kong Rong is carried on using equi-volume impregnating
For 1.06ml/g, specific surface area 387m2/ g, spherical, equivalent diameter 0.5mm), 100 DEG C of dry 6h, 800 DEG C of roasting 6h, system contain
The silica supports of zinc oxide, wherein zinc oxide introduction volume accounts for 10% that catalyst always introduces zinc in mol.It weighs again appropriate
Zinc nitrate is dissolved in deionized water, is carried on the silica supports containing zinc oxide, 100 DEG C of dryings using equi-volume impregnating
Catalyst D-1 is made in 6h, 450 DEG C of roasting 6h.Obtaining catalyst weight group, the weight content in terms of oxide is 20% as ZnO,
450 DEG C or less total acid contents are 0.58mmol/g in catalyst, and 250 DEG C -350 DEG C of acid content accounts for 450 DEG C or less total acid contents
77.5%。
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.
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 2
Take catalyst C-1 not activated, directly progress bromomethane conversion reaction.Unstripped gas is bromomethane and nitrogen mixture
Body, wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed 350h-1。
After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.
1 catalyst reaction performance of table
Claims (30)
1. a kind of preparation method of bromomethane preparing isobutene catalyst, it is characterised in that: comprise the following processes: (1) by zinc oxide
Silica supports are introduced to auxiliary agent oxide zirconium, then high-temperature roasting is handled；(2) remaining zinc oxide is introduced to step
(1) resulting silica supports, then low-temperature bake is handled；(3) bromination processing, bromine are carried out to the carrier after introducing zinc oxide
Changing to zinc oxide weight content is 0.5%-20%, and zinc bromide weight content is 10%-50%.
2. according to the method described in claim 1, it is characterized by: zinc oxide described in step (1) and/or auxiliary agent zirconium oxide draw
Enter to silica supports using impregnation method.
3. according to the method described in claim 2, it is characterized by: using zinc salt, promoter metal zirconium salt solution impregnated carrier, so
Dry afterwards, high-temperature roasting.
4. according to the method described in claim 3, it is characterized by: 60 DEG C -150 DEG C of drying temperature, time 1h-24h, roasting
600 DEG C -1000 DEG C of temperature, time 1h-24h, the zinc oxide amount of introducing described in step (1) accounts for catalyst introducing in mol
Total zinc 1%-20%.
5. according to the method described in claim 4, it is characterized by: 80 DEG C -120 DEG C of drying temperature；Time is 4h-8h, temperature
700 DEG C -900 DEG C, time 4h-8h, the zinc oxide amount of introducing described in step (1) accounts for total zinc of catalyst introducing in mol
5%-15%.
6. according to the method described in claim 1, it is characterized by: zinc oxide is introduced to silica supports and adopts in step (2)
It is introduced with impregnation method.
7. according to the method described in claim 6, it is characterized by: the material obtained using zinc solution impregnation steps (1), warp
Bromomethane preparing isobutene catalyst precarsor is obtained after dry, roasting.
8. according to the method described in claim 7, it is characterized by: 60 DEG C -150 DEG C of drying temperature, time 1h-24h；Roasting
300 DEG C -600 DEG C of temperature, time 1h-24h.
9. according to the method described in claim 8, it is characterized by: 80 DEG C -120 DEG C of drying temperature；Time is 4h-8h；Roasting
400 DEG C -500 DEG C of temperature；Time is 4h-8h.
10. according to the method described in claim 6, it is characterized by: zinc salt is nitrate, hydrochloride, acetate, citrate
One or more of.
11. 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 zinc oxide.
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: the sample for loading zinc oxide is placed in continuous flowing and is fixed
In bed reactor, it is warming up to 150 DEG C -400 DEG C under inert atmosphere, is passed through gas phase bromine-containing compound gas, gas space velocity 50h-1-
1000 h-1；System pressure is 0.1MPa-0.5MPa, and the processing time is 0.5h-8h.
15. according to the method for claim 14, it is characterised in that: be warming up to 180 DEG C -350 DEG C under inert atmosphere, gas space
Speed is 100h-1-500h-1；System pressure is 0.1MPa-0.3MPa, and the processing time is 1h-4h.
16. the catalyst of claim 1 to 15 either method preparation, it is characterised in that: contain zinc oxide, zinc bromide and titanium dioxide
Silicon carrier, zinc oxide weight content are 0.5%-20%；Zinc bromide weight content is 10%-50%；Silica supports weight content
40%-85%。
17. catalyst according to claim 16, it is characterised in that: zinc oxide weight content is 1%-15%；Zinc bromide weight
Amount content is 10%-45%；Silica supports weight content 50%-85%.
18. catalyst according to claim 17, it is characterised in that: zinc oxide weight content is 1%-9%；Zinc bromide weight
Content is 18%-39%；Silica supports weight content 55%-80%.
19. catalyst according to claim 16, it is characterised in that: contain auxiliary agent zirconium in catalyst, zirconium exists based on the element
Weight content in catalyst is 0.1%-10%.
20. catalyst according to claim 19, it is characterised in that: 450 DEG C or less total acid contents are in catalyst
0.5mmol/g-1.3mmol/g, 250 DEG C -350 DEG C of acid content account for the 20%-90% of 450 DEG C or less total acid contents.
21. the application of catalyst described in claim 16, it is characterised in that: including carrying out hydrogen reducing activation to catalyst, make
Content of halogen in catalyst is the 20%-90% for restoring total halogen content in procatalyst, then makes halide and above-mentioned hydrogen
Catalyst contact after gas reduction activation, to prepare isobutene.
22. application according to claim 21, 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%.
23. application according to claim 21, 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.
24. application according to claim 23, 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%.
25. application according to claim 21, 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。
26. application according to claim 25, it is characterised in that: the condition of the contact include reaction temperature be 180 DEG C-
300℃；Reaction pressure is 0.1MPa-3MPa；Air speed is 200h-1-500h-1。
27. application according to claim 21, it is characterised in that: the halide is a halide, dihalo first
One of alkane, three halides are a variety of.
28. application according to claim 21, 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-Hydrogen 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%。
29. application according to claim 28, 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
After managing 4h-8h, hydrogen volume percentage composition is 30%-90% in the gaseous mixture.
30. application according to claim 21, it is characterised in that: the reaction of halide preparing isobutene is in fixed bed, fluidisation
It is carried out in bed, moving bed, slurry bed system or fluidized bed reactor.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4151969A (en) * | 1977-09-12 | 1979-05-01 | Southern Railway Company | System for selectively determining the location of a railway car moving along a railway track |
| 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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2015
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4151969A (en) * | 1977-09-12 | 1979-05-01 | Southern Railway Company | System for selectively determining the location of a railway car moving along a railway track |
| 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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