CN106140211B - A kind of rare-earth element modified halide preparing isobutene catalyst and preparation method thereof - Google Patents
A kind of rare-earth element modified halide preparing isobutene catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of rare-earth element modified halide preparing isobutene catalyst and preparation method thereof.Zinc oxide weight content is 0.5% 20% in the catalyst, and zinc halide weight content is 10% 50%, and samarium oxide weight content is 0.1% 20%, and surplus is alumina catalyst support.Catalyst preparation process includes the following steps：（1）Catalyst precarsor is prepared using coprecipitation；（2）To step（1）Gained catalyst precarsor carries out halogenation treatment, obtains halide preparing isobutene catalyst.The selectivity of halide preparing isobutene can be improved using the catalyst.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof, and it is different to relate in particular to a kind of highly selective system of halide
Catalyst of butylene and preparation method thereof, more particular to a kind of rare-earth element modified halide preparing isobutene catalyst
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
It is in diversified trend to take structure.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, especially 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.Especially in recent years, it develops and uses and grows rapidly in shale gas, if it is possible to produce isobutene from methane, just
An important approach can be provided to obtain isobutene.But methane property is stablized, and it is not easily-activated, become methane chemical utilization
Bottleneck.Domestic and international many researchers carry out methane activation, Study on Transformation one after another, among these, methane after halogen functional groupization again
Transformation technology is expected to become an important breakthrough mouth for solving methane transformation technology problem.
Bromomethane is important methane halides, and one many chemical products can be prepared from bromomethane.Chinese patent CN
101041609A, CN 101284232A disclose it is a kind of by methane in oxygen and HBr/H2Bromo first is converted under the action of O
Alkane, then bromomethane further react the method for generating C3 ~ C13 mixing high-carbon hydrocarbons, the hydrocarbon selective of C5 or more is 70%.
Wherein, HBr is used for methane bromination in first reactor, then discharges in second reactor, is used further to after recovered
In back reaction, the recycling of HBr is realized.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 halide system third
Modified molecular sieve catalyst of alkene and preparation method thereof.By using fluorochemical moditied processing molecular sieve, obtains one kind and contain
There are the catalyst of appropriate microporous structure and acidity, the catalyst that can effectively be catalyzed the reaction that halide is converted into propylene.
Prepared catalyst one way bromomethane conversion ratio in the preparing propylene transformed reaction of bromomethane is 35 ~ 99%, the selectivity of propylene
It is 27 ~ 70%；One way methyl chloride conversion rate is 30 ~ 99% in the preparing propylene transformed reaction of chloromethanes, the selectivity of propylene is 15 ~
70%.Ivan M. Lorkovic et al.（Ivan M. Lorkovic, Aysen Yilmaz, Gurkan A. Yilmaz, et
al. Catalysis Today, 2004, 98, 317-322）It is also proposed that generating bromo with the alkane reaction in bromine and natural gas
Hydrocarbon, then converts bromo-hydrocarbons to dimethyl ether, methanol and metal bromide on metal oxide catalyst, and metal bromide is used
Metal oxide is obtained after oxygen recovery and releases simple substance bromine, completes the cycle of bromine.
Currently, being mainly methanol and dimethyl ether about purpose product in the existing literature of halide conversion, in addition also have
Acetic acid, higher hydrocarbons, ethylene and propylene, and using alkene as in the technology of target product, product is mostly ethylene, propylene, and single
One selectivity of product is not high, and not yet finds 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 rare-earth element modified halide preparing isobutene catalyst
And its preparation method and application.
A kind of rare-earth element modified halide preparing isobutene catalyst, zinc oxide weight content is in the catalyst
0.5%-20%, preferably 1%-15%, further preferred 1%-9%；Zinc halide weight content is 10%-50%, preferably 15%-45%, into one
Walk preferred 18%-39%；Samarium oxide weight content is 0.1%-20%, preferably 0.1%-15%, further preferably 0.5%-10%；It is remaining
Amount is alumina catalyst support.
In above-mentioned halide preparing isobutene catalyst, 450 DEG C or less total acid contents（NH3-TPD）For 0.5mmol/g-
1.3mmol/g, preferably 0.6mmol/g-1.2mmol/g, more preferable 0.7mmol-1.1mmol/g；250 DEG C -350 DEG C of acid content
Account for the 20%-90% of 450 DEG C or less total acid contents, preferably 30%-80%, more preferable 40%-80%.
The present invention provides the preparation method of above-mentioned catalyst, includes the following steps：
（1）Zinc precursor, samarium presoma and support precursor are dissolved in the water and are configured to the solution that pH value is 1 ~ 3；
At 40 ~ 80 DEG C, alkaline solution is slowly added dropwise and is co-precipitated, the pH value that mother liquor is controlled in precipitation process is 8 ~ 11；Precipitation terminates
Afterwards, aging is stood, is then filtered, washed, catalyst precarsor can be made after drying, roasting；
（2）To step（1）The catalyst precarsor of gained carries out halogenation treatment, and halide preparing isobutene catalyst is made.
The method of the present invention step（1）In, the zinc precursor, samarium presoma, support precursor are nitrate, sulfuric acid
Salt, halide etc., preferably nitrate；The alkaline solution is sodium carbonate, sodium bicarbonate, ammonium hydroxide etc., preferably ammonium hydroxide.
The method of the present invention step（1）Described in ageing process can be aged at room temperature, or in certain constant temperature item
Aging under part, aging temperature be 10 DEG C -90 DEG C, preferably 70 DEG C -90 DEG C, ageing time 1h-24h, preferably 6h-10h.
The method of the present invention, step（1）In further include dry and roasting process.Drying temperature is 50 DEG C -200 DEG C, preferably
60 DEG C -150 DEG C, more preferably 80 DEG C -120 DEG C；Drying time is 1h-48h, preferably 2h-36h, more preferably 2h-24h；It is dry
Can be vacuum drying when dry, or it is dry under the conditions of inert gas shielding, it can also dry in air atmosphere；Roasting
Temperature is 200 DEG C -800 DEG C, preferably 300 DEG C -600 DEG C, more preferably 350 DEG C -500 DEG C；Roasting time is 1h-24h, preferably
For 2h-16h, more preferably 4h-8h；Can be to be dry under the conditions of inert gas shielding when roasting, it can also be in air atmosphere
It is dry.
The method of the present invention, step（2）Middle halogenation treatment process is as follows：By step（1）It is solid that resulting material is placed in continuous flowing
In fixed bed reactor, 150 DEG C -400 DEG C, preferably 180 DEG C -350 DEG C, more preferably 200 DEG C -300 are warming up under inert atmosphere
℃；Halide and inert gas gaseous mixture are then passed to, halide volumn concentration is 1%-95% in gaseous mixture, preferably
For 10%-90%, surplus is inert gas；Processing time is 0.5h-16h, preferably 1h-8h, more preferably 1h-4h；Processing pressure
Power is 0.1MPa-0.5MPa, preferably 0.1MPa-0.3MPa；Volume space velocity is 50h-1-1000 h-1, preferably 100 h-1-
500 h-1。
The application of above-mentioned halide preparing isobutene catalyst, using halide as raw material, reaction temperature is 150 DEG C -350
DEG C, preferably 180 DEG C -300 DEG C, more preferably 200 DEG C -270 DEG C；Reaction pressure is 0.1MPa-5MPa, preferably 0.1MPa-
3MPa；Air speed is 50h-1-1000h-1, preferably 200h-1-500h-1, need to carry out reduction treatment, reduction to catalyst before charging
It is 20%-90%, the preferably 30%-80% for restoring total halogen content in procatalyst to the content of halogen in catalyst, it is further excellent
Select 40%-80%.
In above application, a kind of specific reduction treatment process is as follows：Under inert atmosphere by catalyzer temperature-elevating to 300 DEG C-
600 DEG C, preferably 350 DEG C -550 DEG C；It is 200h to then pass to air speed-1-2000h-1, preferably 500h-1-1000h-1Hydrogen
Or the mixed gas of hydrogen and inert gas, 2h-16h is handled in 0.1MPa-0.5MPa, preferably 0.1MPa-0.3MPa, 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 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 that nitrogen, argon gas, helium etc. are not sent out under the conditions of involved in the present invention in above application
The gas of biochemical reaction, preferably nitrogen.
In above application, halide raw material can be a halide, methylene halide, three halides, preferably
One bromomethane, methylene bromide, bromoform, more preferably a bromomethane.
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 reactor of the forms such as slurry bed system or ebullated bed, preferably fixed bed, fluid bed
Reactor.
Compared with prior art, method of the present invention can by bromomethane it is highly selective be converted into isobutene.It presses
The halide preparing isobutene catalyst that the method for the present invention is prepared using co-precipitation, by controlling deposition condition and subsequent step,
The samarium oxide and alumina support that can make addition realize combining closely for molecular level, improve the corrosion resistance of catalyst；Together
When, Zn elements and the dispersion degree in activated centre can also be improved using this method, improve the activity of catalyst.The present invention relates to
Bromomethane conversion preparing isobutene method for preparing catalyst is simple, is easy to industrialize.Bromomethane of the present invention converts preparing isobutene method
Have many advantages, such as that reaction condition is mild, selectivity of product is high, industrialization easy to implement, application prospect is boundless.
Specific implementation mode
The technology contents and effect further illustrated the present invention with reference to embodiment, but do not limit the present invention.Catalyst
Acidimetric estimation uses NH3- TPD methods, the instrument model used is 2920 chemistry of MICROMERITICS companies of U.S. AutoChem
Adsorption instrument, specific continuous mode are as follows：Sample is cooled to 150 DEG C after 1 hour with helium purge at 450 DEG C, introduces ammonia and helium
The mixed gas of gas, ammonia volume content 10%, Pulse adsorption reach balance five times；Helium purge 2 hours, then with 10 DEG C/min
Heating rate temperature programming carry out ammonia be desorbed to 450 DEG C；Ammonia after desorption is detected using TCD detectors, quantitative to calculate catalysis
Agent Surface acidity.
Embodiment 1
It weighs appropriate zinc nitrate, samaric nitrate, aluminum nitrate to be dissolved completely in deionized water, adjusting solution ph with nitric acid is
1~3；At 40 ~ 80 DEG C, 25 wt% ammonium hydroxide being slowly added dropwise and are co-precipitated, the pH value that mother liquor is controlled in precipitation process is 8 ~ 11,
The suspension of generation stands aging 6 hours at 70 DEG C；The sediment of gained is put into baking oven after being filtered, washed in 80 DEG C
It is roasted 8 hours at lower drying 24 hours, 400 DEG C；Catalyst precarsor ZnO-SmO/Al is made2O3.It is anti-using continuous flow fixed bed
Device to be answered, catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 30% in monobromo methane blended gas,
Surplus is nitrogen, and treatment conditions are 250 DEG C, 0.1MPa, 100h-1, time 2h.Catalyst is made, weight group becomes ZnBr2
Content is 31.2%, ZnO content 3.7%, and Sm contents in terms of oxide are 5%, and 450 DEG C or less total acid contents are in catalyst
0.84mmol/g, 250 DEG C -350 DEG C of acid content account for the 52.25% 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,
Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 50%, and reaction temperature is 230 DEG C, reaction
Pressure is 1MPa（Absolute pressure）, air speed 500h-1, it is passed through unstripped gas procatalyst and activates in a hydrogen atmosphere, reducing condition 400
DEG C, 0.2MPa（Absolute pressure）, 1000h-1, recovery time 4h, it is halogen in reduction procatalyst to restore the content of halogen in rear catalyst
The 65.28% of plain total content.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 95.78%, selective isobutene
87.65%。
Embodiment 2
It weighs appropriate zinc nitrate, samaric nitrate, aluminum nitrate to be dissolved completely in deionized water, adjusting solution ph with nitric acid is
1~3；At 40 ~ 80 DEG C, 25 wt% ammonium hydroxide being slowly added dropwise and are co-precipitated, the pH value that mother liquor is controlled in precipitation process is 8 ~ 11,
The suspension of generation stands aging 8 hours at 80 DEG C；The sediment of gained is put into baking oven after being filtered, washed in 100 DEG C
It is roasted 4 hours at lower drying 16 hours, 450 DEG C；Catalyst precarsor ZnO-SmO/Al is made2O3.It is anti-using continuous flow fixed bed
Device to be answered, catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 50% in monobromo methane blended gas,
Surplus is nitrogen, and treatment conditions are 230 DEG C, 0.2MPa, 200h-1, time 4h.Catalyst is made, weight group becomes ZnBr2
Content is 8.7%, ZnO content 1.6%, and Sm contents in terms of oxide are 5%.450 DEG C or less total acid contents are in catalyst
0.6mmol/g, 250 DEG C -350 DEG C of acid content account for the 64.01% 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,
Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, reaction
Pressure is 2MPa（Absolute pressure）, air speed 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing
Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa（Absolute pressure）, 800h-1, recovery time 4h, after reduction
Content of halogen in catalyst is restore total halogen content in procatalyst 51.7%.After stable reaction one hour, sampling point
Analysis.Bromomethane conversion ratio 68.69%, selective isobutene 66.92%.
Embodiment 3
It weighs appropriate zinc nitrate, samaric nitrate, aluminum nitrate to be dissolved completely in deionized water, adjusting solution ph with nitric acid is
1~3；At 40 ~ 80 DEG C, 25 wt% ammonium hydroxide being slowly added dropwise and are co-precipitated, the pH value that mother liquor is controlled in precipitation process is 8 ~ 11,
The suspension of generation stands aging 10 hours at 90 DEG C；The sediment of gained is put into baking oven after being filtered, washed in 120
It is roasted 8 hours at drying 12 hours, 350 DEG C at DEG C；Catalyst precarsor ZnO-SmO/Al is made2O3.Use continuous flow fixed bed
Reactor handles catalyst precarsor under monobromo methane atmosphere, and monobromo methane volumetric content is in monobromo methane blended gas
70%, surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, time 2h.Catalyst is made, weight group becomes
ZnBr2Content is 17.3%, ZnO content 3.1%, and Sm contents in terms of oxide are 5%.450 DEG C or less total acid contents are in catalyst
0.73mmol/g, 250 DEG C -350 DEG C of acid content account for the 59% 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,
Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 80%, and reaction temperature is 200 DEG C, reaction
Pressure is 3MPa（Absolute pressure）, air speed 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing
Hydrogen volume content is 50% in gas, and reducing condition is 500 DEG C, 0.1MPa（Absolute pressure）, 500h-1, recovery time 4h, after reduction
Content of halogen in catalyst is restore total halogen content in procatalyst 45.66%.After stable reaction one hour, sampling point
Analysis.Bromomethane conversion ratio 90.71%, selective isobutene 83.68%.
Embodiment 4
It weighs appropriate zinc nitrate, samaric nitrate, aluminum nitrate to be dissolved completely in deionized water, adjusting solution ph with nitric acid is
1~3；At 40 ~ 80 DEG C, 25 wt% ammonium hydroxide being slowly added dropwise and are co-precipitated, the pH value that mother liquor is controlled in precipitation process is 8 ~ 11,
The suspension of generation stands aging 6 hours at 80 DEG C；The sediment of gained is put into baking oven after being filtered, washed in 120 DEG C
It is roasted 8 hours at lower drying 12 hours, 350 DEG C；Catalyst precarsor ZnO-SmO/Al is made2O3.It is anti-using continuous flow fixed bed
Device to be answered, catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 50% in monobromo methane blended gas,
Surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, time 2h.Catalyst is made, weight group becomes ZnBr2
Content is 20.8%, ZnO content 5.6%, and Sm contents in terms of oxide are 2%.450 DEG C or less total acid contents are in catalyst
0.81mmol/g, 250 DEG C -350 DEG C of acid content account for the 40.31% 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,
Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 30%, and reaction temperature is 270 DEG C, reaction
Pressure is 2MPa（Absolute pressure）, air speed 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing
Hydrogen volume content is 70% in gas, and reducing condition is 350 DEG C, 0.3MPa（Absolute pressure）, 800h-1, recovery time 6h, after reduction
Content of halogen in catalyst is restore total halogen content in procatalyst 55.9%.After stable reaction one hour, sampling point
Analysis.Bromomethane conversion ratio 85.63%, selective isobutene 72.08%.
Embodiment 5
It weighs appropriate zinc nitrate, samaric nitrate, aluminum nitrate to be dissolved completely in deionized water, adjusting solution ph with nitric acid is
1~3；At 40 ~ 80 DEG C, 25 wt% ammonium hydroxide being slowly added dropwise and are co-precipitated, the pH value that mother liquor is controlled in precipitation process is 8 ~ 11,
The suspension of generation stands aging 6 hours at 80 DEG C；The sediment of gained is put into baking oven after being filtered, washed in 120 DEG C
It is roasted 8 hours at lower drying 12 hours, 350 DEG C；Catalyst precarsor ZnO-SmO/Al is made2O3.It is anti-using continuous flow fixed bed
Device to be answered, catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 50% in monobromo methane blended gas,
Surplus is nitrogen, and treatment conditions are 200 DEG C, 0.1MPa, 100h-1, time 4h.Catalyst is made, weight group becomes ZnBr2
Content is 26%, ZnO content 4.7%, and Sm contents in terms of oxide are 10%.450 DEG C or less total acid contents are in catalyst
0.95mmol/g, 250 DEG C -350 DEG C of acid content account for the 50.32% 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,
Unstripped gas is a bromomethane, and reaction temperature is 270 DEG C, reaction pressure 2MPa（Absolute pressure）, air speed 350h-1.It is passed through unstripped gas
Before, catalyst activates under the mixed atmosphere of hydrogen, and hydrogen volume content is 60% in mixed gas, reducing condition 550
DEG C, 0.3MPa（Absolute pressure）, 800h-1, recovery time 8h, it is halogen in reduction procatalyst to restore the content of halogen in rear catalyst
The 40% of total content.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 94.81%, selective isobutene 84.64%.
Embodiment 6
It weighs appropriate zinc nitrate, samaric nitrate, aluminum nitrate to be dissolved completely in deionized water, adjusting solution ph with nitric acid is
1~3；At 40 ~ 80 DEG C, 25 wt% ammonium hydroxide being slowly added dropwise and are co-precipitated, the pH value that mother liquor is controlled in precipitation process is 8 ~ 11,
The suspension of generation stands aging 6 hours at 80 DEG C；The sediment of gained is put into baking oven after being filtered, washed in 120 DEG C
It is roasted 8 hours at lower drying 12 hours, 350 DEG C；Catalyst precarsor ZnO-SmO/Al is made2O3.It is anti-using continuous flow fixed bed
Device to be answered, catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 30% in monobromo methane blended gas,
Treatment conditions are 250 DEG C, 0.1MPa, 100h-1, time 2h.Catalyst is made, weight group becomes ZnBr2Content is
31.2%, ZnO content 3.7%, Sm contents in terms of oxide are 5%.450 DEG C or less total acid contents are 0.79mmol/g in catalyst,
250 DEG C -350 DEG C of acid content accounts for the 66.18% 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,
Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 50%, and reaction temperature is 230 DEG C, reaction
Pressure is 0.1MPa（Absolute pressure）, air speed 500h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixes
It is 80% to close hydrogen volume content in gas, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, 1000h-1, recovery time 4h, reduction
Content of halogen in rear catalyst is restore total halogen content in procatalyst 56.46%.After stable reaction one hour, sampling
Analysis.Bromomethane conversion ratio 57.54%, selective isobutene 74.15%.
Embodiment 7
It weighs appropriate zinc nitrate, samaric nitrate, aluminum nitrate to be dissolved completely in deionized water, adjusting solution ph with nitric acid is
1~3；At 40 ~ 80 DEG C, 25 wt% ammonium hydroxide being slowly added dropwise and are co-precipitated, the pH value that mother liquor is controlled in precipitation process is 8 ~ 11,
The suspension of generation stands aging 6 hours at 80 DEG C；The sediment of gained is put into baking oven after being filtered, washed in 120 DEG C
It is roasted 8 hours at lower drying 12 hours, 350 DEG C；Catalyst precarsor ZnO-SmO/Al is made2O3.It is anti-using continuous flow fixed bed
Device to be answered, catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 30% in monobromo methane blended gas,
Surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, time 4h.Catalyst is made, weight group becomes ZnBr2
Content is 15.6%, ZnO content 6.5%, and Sm contents in terms of oxide are 5%.450 DEG C or less total acid contents are in catalyst
0.85mmol/g, 250 DEG C -350 DEG C of acid content account for the 60.6% 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,
Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, reaction
Pressure is 2MPa（Absolute pressure）, air speed 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing
Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa（Absolute pressure）, 800h-1, recovery time 4h, after reduction
Content of halogen in catalyst is restore total halogen content in procatalyst 60.64%.After stable reaction one hour, sampling point
Analysis.Bromomethane conversion ratio 72.04%, selective isobutene 69.05%.
Embodiment 8
It weighs appropriate zinc nitrate, samaric nitrate, aluminum nitrate to be dissolved completely in deionized water, adjusting solution ph with nitric acid is
1~3；At 40 ~ 80 DEG C, 25 wt% ammonium hydroxide being slowly added dropwise and are co-precipitated, the pH value that mother liquor is controlled in precipitation process is 8 ~ 11,
The suspension of generation stands aging 6 hours at 80 DEG C；The sediment of gained is put into baking oven after being filtered, washed in 120 DEG C
It is roasted 8 hours at lower drying 12 hours, 350 DEG C；Catalyst precarsor ZnO-SmO/Al is made2O3.It is anti-using continuous flow fixed bed
Device to be answered, catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 30% in monobromo methane blended gas,
Surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, time 4h.Catalyst is made, weight group becomes ZnBr2
Content is 20.8%, ZnO content 5.6%, and Smr contents in terms of oxide are 5%.450 DEG C or less total acid contents are in catalyst
0.82mmol/g, 250 DEG C -350 DEG C of acid content account for the 54.58% 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,
Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, reaction
Pressure is 2MPa（Absolute pressure）, air speed 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing
Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa（Absolute pressure）, 800h-1, recovery time 4h, after reduction
Content of halogen in catalyst is restore total halogen content in procatalyst 61.62%.After stable reaction one hour, sampling point
Analysis.Bromomethane conversion ratio 78.95%, selective isobutene 83.68%.
Embodiment 9
It weighs appropriate zinc nitrate, samaric nitrate, aluminum nitrate to be dissolved completely in deionized water, adjusting solution ph with nitric acid is
1~3；At 40 ~ 80 DEG C, 25 wt% ammonium hydroxide being slowly added dropwise and are co-precipitated, the pH value that mother liquor is controlled in precipitation process is 8 ~ 11,
The suspension of generation stands aging 6 hours at 80 DEG C；The sediment of gained is put into baking oven after being filtered, washed in 120 DEG C
It is roasted 8 hours at lower drying 12 hours, 350 DEG C；Catalyst precarsor ZnO-SmO/Al is made2O3.It is anti-using continuous flow fixed bed
Device to be answered, catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 30% in monobromo methane blended gas,
Surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, time 4h.Catalyst is made, weight group becomes ZnBr2
Content is 36.3%, ZnO content 2.8%, and Sm contents in terms of oxide are 5%.450 DEG C or less total acid contents are in catalyst
0.98mmol/g, 250 DEG C -350 DEG C of acid content account for the 56.66% 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,
Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, reaction
Pressure is 2MPa（Absolute pressure）, air speed 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing
Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa（Absolute pressure）, 800h-1, recovery time 4h, after reduction
Content of halogen in catalyst is restore total halogen content in procatalyst 37.84%.After stable reaction one hour, sampling point
Analysis.Bromomethane conversion ratio 69.59%, selective isobutene 58.19%.
Embodiment 10
It weighs appropriate zinc nitrate, samaric nitrate, aluminum nitrate to be dissolved completely in deionized water, adjusting solution ph with nitric acid is
1~3；At 40 ~ 80 DEG C, 25 wt% ammonium hydroxide are slowly added dropwise and are co-precipitated, the pH value for controlling mother liquor is 8 ~ 11, the suspension of generation
Liquid stands aging 6 hours at 80 DEG C；It is small to be put into baking oven at 120 DEG C dry 12 after being filtered, washed for the sediment of gained
When, it roasts 8 hours at 350 DEG C；Catalyst precarsor ZnO-SmO/Al is made2O3.Using continuous fixed bed reactor, one
Catalyst precarsor is handled under bromomethane atmosphere, monobromo methane volumetric content is 30% in monobromo methane blended gas, and surplus is nitrogen
Gas, treatment conditions are 230 DEG C, 0.1MPa, 100h-1, time 4h.Catalyst is made, weight group becomes ZnBr2Content is
35.9%, ZnO content 3.1%, Sm contents in terms of oxide are 5%.450 DEG C or less total acid contents are 1.03mmol/g in catalyst,
250 DEG C -350 DEG C of acid content accounts for the 63.42% 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,
Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 80%, and reaction temperature is 200 DEG C, reaction
Pressure is 3MPa（Absolute pressure）, air speed 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing
Hydrogen volume content is 90% in gas, and reducing condition is 500 DEG C, 0.1MPa（Absolute pressure）, 500h-1, recovery time 6h, after reduction
Content of halogen in catalyst is restore total halogen content in procatalyst 50.22%.After stable reaction one hour, sampling point
Analysis.Bromomethane conversion ratio 37.44%, selective isobutene 42.08%.
Comparative example 1
Catalyst preparation is the same as embodiment 5.Evaluating catalyst condition with embodiment 5, the difference is that, do not carry out at activation
Reason.After reaction one hour, sampling analysis.Bromomethane conversion ratio 2.81%, selective isobutene 0.
Comparative example 2
Catalyst preparation with embodiment 5, the difference is that, do not carry out halogenation treatment.Evaluating catalyst condition is the same as implementation
Example 5, after reacting one hour, sampling analysis.Bromomethane conversion ratio 97.54%, selective isobutene 0.
Comparative example 3
Catalyst preparation is the same as embodiment 5.Evaluating catalyst condition with embodiment 5, the difference is that, by zinc bromide whole
It is reduced to zinc.After reaction one hour, sampling analysis.Bromomethane conversion ratio 2.05%, selective isobutene 0.
Claims (20)
1. a kind of rare-earth element modified halide preparing isobutene catalyst, it is characterised in that：Zinc oxide weight in the catalyst
Amount content is 0.5%-20%, and zinc halide weight content is 10%-50%, and samarium oxide weight content is 0.1%-20%, and surplus is carrier
Aluminium oxide.
2. catalyst according to claim 1, it is characterised in that：Zinc oxide weight content is 1%- in the catalyst
15%；Zinc halide weight content is 15%-45%；Samarium oxide weight content is 0.1%-15%.
3. catalyst according to claim 1, it is characterised in that：Zinc oxide weight content is 1%-9% in the catalyst；
Zinc halide weight content is 18%-39%；Samarium oxide weight content is 0.5%-10%.
4. catalyst according to claim 1, it is characterised in that：450 DEG C or less total acid contents are 0.5mmol/ in catalyst
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.
5. catalyst according to claim 4, it is characterised in that：450 DEG C or less total acid contents are 0.6mmol/ in catalyst
G-1.2mmol/g, 250 DEG C -350 DEG C of acid content account for the 30%-80% of 450 DEG C or less total acid contents.
6. catalyst according to claim 5, it is characterised in that：450 DEG C or less total acid contents are 0.7mmol- in catalyst
1.1mmol/g, 250 DEG C -350 DEG C of acid content account for the 40%-80% of 450 DEG C or less total acid contents.
7. the preparation method of catalyst described in claim 1, it is characterised in that：Including following preparation process：
（1）Zinc precursor, samarium presoma and support precursor are dissolved in the water and are configured to the solution that pH value is 1 ~ 3；40 ~ 80
At DEG C, alkaline solution is slowly added dropwise and is co-precipitated, the pH value that mother liquor is controlled in precipitation process is 8 ~ 11；It is quiet after precipitation
Aging is set, is then filtered, washed, catalyst precarsor can be made after drying, roasting；
（2）To step（1）Resulting material carries out halogenation treatment, and halide preparing isobutene catalyst is made.
8. according to the method described in claim 7, it is characterized in that：Step（1）Middle zinc, samarium, support precursor are nitrate, sulphur
Hydrochlorate or halide；The alkaline solution is sodium carbonate liquor, sodium bicarbonate solution or ammonium hydroxide.
9. according to the method described in claim 7, it is characterized in that：Step（1）Middle aging temperature is 10 DEG C -90 DEG C, when aging
Between be 1h-24h.
10. according to the method described in claim 7, it is characterized in that：Step（1）Include dry and roasting process, dry temperature
Degree is 50 DEG C -200 DEG C；Drying time is 1h-48h；Calcination temperature is 200 DEG C -800 DEG C；Roasting time is 1h-24h.
11. according to the method described in claim 7, it is characterized in that：Step（2）Described in halogenation treatment process it is as follows：It will step
Suddenly（1）Sample be placed in continuous fixed bed reactor, 150 DEG C -400 DEG C are warming up under inert atmosphere, is passed through halogenated first
Alkane and noble gas mixtures, halide volumn concentration is 1%-95% in gaseous mixture；Gas space velocity is 50h-1-1000
h-1；Processing pressure is 0.1MPa-0.5MPa, processing time 0.5h-8h.
12. according to the method for claim 11, it is characterised in that：180 DEG C -350 DEG C are warming up under inert atmosphere, gas space
Speed is 100h-1-500h-1；Processing pressure is 0.1MPa-0.3MPa, processing time 1h-4h.
13. the application of catalyst described in claim 1, it is characterised in that：Using halide as raw material, reaction temperature be 150 DEG C-
350℃；Reaction pressure is 0.1MPa-5MPa；Air speed is 50h-1-1000h-1, need to carry out also original place to catalyst before charging
Reason, it is the 20%-90% for restoring total halogen content in procatalyst to be restored to the content of halogen in catalyst.
14. application according to claim 13, it is characterised in that：Reaction temperature is 180 DEG C -300 DEG C；Reaction pressure is
0.1MPa-3MPa；Air speed is 200h-1-500h-1, it is that halogen is total in reduction procatalyst to be restored to the content of halogen in catalyst
The 30%-80% of content.
15. application according to claim 13, it is characterised in that：Reduction treatment process is as follows：It will catalysis under inert atmosphere
Agent is warming up to 300 DEG C -600 DEG C；It is 200h to then pass to air speed-1-2000h-1Hydrogen or hydrogen and inert gas gaseous mixture
Body handles 2h-16h at 0.1MPa-0.5Mpa, is down to reaction temperature and is passed through halide and is reacted, hydrogen in gaseous mixture
Volumn concentration is 10%-95%.
16. application according to claim 15, it is characterised in that：By catalyzer temperature-elevating to 350 DEG C -550 under inert atmosphere
℃；It is 500h to then pass to air speed-1-1000h-1Hydrogen or hydrogen and inert gas mixed gas, in 0.1MPa-
4h-8h is handled under 0.3Mpa, hydrogen volume percentage composition is 30%-90% in the gaseous mixture.
17. application according to claim 13, it is characterised in that：Raw material is the gaseous mixture of halide and inert atmosphere
Body, the volumetric concentration of halide is 10%-90% in mixed gas.
18. application according to claim 17, it is characterised in that：Inert atmosphere be nitrogen, argon gas, one kind in helium or
It is several.
19. application according to claim 13, it is characterised in that：Halide is a halide, methylene halide, three
One or more of halide.
20. application according to claim 19, it is characterised in that：Halide is a bromomethane, methylene bromide, tribromo first
One or more of alkane.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4154969A (en) * | 1977-03-24 | 1979-05-15 | Monsanto Company | Production of dihydroxydiphenyl alkanes |
| CN1502411A (en) * | 2002-11-20 | 2004-06-09 | ��Խ��ѧ��ҵ��ʽ���� | Zinc chloride-loaded support and method for producing the same |
| CN100582064C (en) * | 2006-03-20 | 2010-01-20 | 微宏科技（湖州）有限公司 | Flow process for synthesizing C3 to C13 high hydrocarbons by methane through non-synthetic gas method |
-
2015
- 2015-03-27 CN CN201510135800.9A patent/CN106140211B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4154969A (en) * | 1977-03-24 | 1979-05-15 | Monsanto Company | Production of dihydroxydiphenyl alkanes |
| CN1502411A (en) * | 2002-11-20 | 2004-06-09 | ��Խ��ѧ��ҵ��ʽ���� | Zinc chloride-loaded support and method for producing the same |
| CN100582064C (en) * | 2006-03-20 | 2010-01-20 | 微宏科技（湖州）有限公司 | Flow process for synthesizing C3 to C13 high hydrocarbons by methane through non-synthetic gas method |
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