CN106140211A - 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.In described catalyst, zinc oxide weight content is 0.5%-20%, and zinc halide weight content is 10%-50%, and Disamarium trioxide weight content is 0.1%-20%, and surplus is alumina catalyst support.Catalyst preparation process comprises the steps: that (1) uses coprecipitation to prepare catalyst precarsor；(2) step (1) gained catalyst precarsor is carried out halogenation treatment, obtain halide preparing isobutene catalyst.Use this catalyst can improve the selectivity of halide preparing isobutene.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof, relate in particular to catalyst of a kind of halide height selectivity preparing isobutene and preparation method thereof, 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 its derived product is numerous, and vertical industry chain is complicated, and consumption structure is diversified trend.Multiple high value-added product can be prepared for raw material, such as: multiple Organic Chemicals and the fine chemistry products such as butyl rubber, polyisobutylene, methyl tertiary butyl ether(MTBE), isoprene and lucite with isobutene..Owing to the market scale of isobutene. downstream product constantly expands, its imbalance between supply and demand will gradually highlight, and particularly under the background of petroleum resources exhaustion day by day, the yield of isobutene. has become the critical bottleneck of restriction downstream industry development.Therefore, the isobutene. syntheti c route of exploitation Non oil-based route, extremely the most urgent.
Methane is the main component of natural gas, the important research content during therefore methane trans-utilization just becomes gas chemical industry's technology.The most in recent years, develop fast development at shale gas, if it is possible to produce isobutene. from methane, an important approach will be provided for obtaining isobutene..But methane stable in properties, the most easily-activated, become the bottleneck of methane chemical utilization.Both at home and abroad many researcheres carry out methane activation, Study on Transformation one after another, among these, methane transformation technology again after halogen functional groupization, it is expected to become an important breakthrough mouth of a solution methane transformation technology difficult problem.
Bromomethane is important methane halides, can the many chemical products of preparation from bromomethane.Chinese patent CN 101041609A, CN 101284232A disclose one by methane at oxygen and HBr/H2Being converted into bromomethane under the effect of O, then bromomethane reacts the method generating C3 ~ C13 mixing high-carbon hydrocarbon further, and the hydrocarbon selective of more than C5 is 70%.Wherein, HBr for methane bromination, then discharges in first reactor in second reactor, recovered after be used further in back reaction, it is achieved the recycling of HBr.(CN 102527427A, the Jieli such as Wang Ye
He, Ting Xu, Zhihui Wang, et.al. Angew. Chem. Int. Ed. 2012,51,2438-2442) modified molecular sieve catalyst disclosing a kind of halide propylene and preparation method thereof.By using fluorochemical moditied processing molecular sieve, obtaining a kind of containing appropriate microporous structure and the catalyst of acidity, this catalyst can effectively be catalyzed halide and be converted into the reaction of propylene.Prepared catalyst one way bromomethane conversion ratio in the reaction that bromomethane is preparing propylene transformed is 35 ~ 99%, and the selectivity of propylene is 27 ~ 70%；In the reaction that chloromethanes is preparing propylene transformed, one way methyl chloride conversion rate is 30 ~ 99%, and the selectivity of propylene is 15 ~ 70%.Ivan M. Lorkovic et al. (Ivan M. Lorkovic, Aysen Yilmaz, Gurkan A. Yilmaz, et al.
Catalysis Today, 2004,98,317-322) it is also proposed that generate bromo-hydrocarbons with bromine with the alkane reaction in natural gas, then on metal oxide catalyst, bromo-hydrocarbons is converted into dimethyl ether, methanol and metal bromide, obtain metal-oxide after metal bromide oxygen recovery and discharge simple substance bromine, completing the circulation of bromine.
At present, it is mainly methanol and dimethyl ether about purpose product in the existing document that halide converts, additionally also have acetic acid, higher hydrocarbons, ethylene and propylene, and in the technology with alkene as target product, product mostly is ethylene, propylene, and single selectivity of product is the highest, and not yet find the relevant report of bromomethane high selectivity isobutene..
Summary of the invention
For the deficiencies in 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, in described catalyst, zinc oxide weight content is 0.5%-20%, preferably 1%-15%, further preferred 1%-9%；Zinc halide weight content is 10%-50%, preferably 15%-45%, further preferred 18%-39%；Disamarium trioxide weight content is 0.1%-20%, preferably 0.1%-15%, more preferably 0.5%-10%；Surplus is alumina catalyst support.
In above-mentioned halide preparing isobutene catalyst, less than 450 DEG C total acid content (NH3-TPD) it is 0.5mmol/g-1.3mmol/g, preferably 0.6mmol/g-1.2mmol/g, more preferably 0.7mmol-1.1mmol/g；The acid content of 250 DEG C-350 DEG C accounts for the 20%-90% of less than 450 DEG C total acid contents, preferably 30%-80%, more preferably 40%-80%.
The present invention provides the preparation method of above-mentioned catalyst, comprises the steps:
(1) zinc precursor, samarium presoma and support precursor are dissolved in the water it are configured to the solution that pH value is 1 ~ 3；At 40 ~ 80 DEG C, being slowly added dropwise alkaline solution and be co-precipitated, the pH value controlling mother solution in precipitation process is 8 ~ 11；After precipitation terminates, stand aging, then filter, wash, through being dried, catalyst precarsor can be prepared after roasting；
(2) catalyst precarsor of step (1) gained is carried out halogenation treatment, prepare halide preparing isobutene catalyst.
In the inventive method step (1), described zinc precursor, samarium presoma, support precursor are nitrate, sulfate, halogenide etc., preferably nitrate；Described alkaline solution is sodium carbonate, sodium bicarbonate, ammonia etc., preferably ammonia.
Ageing process described in the inventive method step (1) can be aged at room temperature, it is also possible to for aging under certain constant temperature, and aging temperature is 10 DEG C-90 DEG C, preferably 70 DEG C-90 DEG C, and ageing time is 1h-24h, preferably 6h-10h.
The inventive method, also includes in step (1) being dried and roasting process.Baking temperature is 50 DEG C-200 DEG C, preferably 60 DEG C-150 DEG C, more preferably 80 DEG C-120 DEG C；Drying time is 1h-48h, preferably 2h-36h, more preferably 2h-24h；Can be vacuum drying time dry, it is also possible to for being dried under the conditions of inert gas shielding, it is also possible to be dried in air atmosphere；Sintering temperature is 200 DEG C-800 DEG C, preferably 300 DEG C-600 DEG C, more preferably 350 DEG C-500 DEG C；Roasting time is 1h-24h, preferably 2h-16h, more preferably 4h-8h；Can be to be dried under the conditions of inert gas shielding during roasting, it is also possible to be dried in air atmosphere.
The inventive method, in step (2), halogenation treatment process is as follows: be placed in continuous fixed bed reactor by step (1) gained material, 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；Then passing to halide and noble gas gaseous mixture, in gaseous mixture, halide volumn concentration is 1%-95%, preferably 10%-90%, and surplus is noble gas；The process time is 0.5h-16h, preferably 1h-8h, more preferably 1h-4h；Processing pressure 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, with halide as raw material, reaction temperature is 150 DEG C-350 DEG C, preferably 180 DEG C-300 DEG C, more preferably 200 DEG C-270 DEG C；Reaction pressure is 0.1MPa-5MPa, preferably 0.1MPa-3MPa；Air speed is 50h-1-1000h-1, preferably 200h-1-500h-1, needing before charging catalyst is carried out reduction treatment, the content of halogen being reduced in catalyst is the 20%-90%, preferably 30%-80%, further preferred 40%-80% of total halogen content in reduction procatalyst.
In above-mentioned application, a kind of concrete reduction treatment process is as follows: by catalyzer temperature-elevating to 300 DEG C-600 DEG C under inert atmosphere, preferably 350 DEG C-550 DEG C；Then passing to air speed is 200h-1-2000h-1, preferably 500h-1-1000h-1Hydrogen or the mixed gas of hydrogen and noble gas, at 0.1MPa-0.5MPa, after preferably 0.1MPa-0.3MPa processes 2h-16h, preferably 4h-8h, be down to reaction temperature and be passed through halide and react.In described gaseous mixture, hydrogen volume percentage composition is 10%-95%, preferably 30%-90%, more preferably 50%-90%.
In above-mentioned application, raw material can also be the mixed gas of halide and noble gas, and in mixed gas, the volumetric concentration of halide is 10%-90%, preferably 30%-80%.
Noble gas involved in above-mentioned application is the gas that nitrogen, argon, helium etc. do not occur chemical reaction under the conditions of involved in the present invention, preferably nitrogen.
In above-mentioned application, halide raw material can be a halide, methylene halide, three halides, preferably one bromomethane, methylene bromide, bromoform, more preferably one bromomethane.
In above-mentioned application, the reaction of halide preparing isobutene can be carried out, such as fixed bed, fluid bed, fixed fluidized bed, moving bed, the reactor of the form such as slurry bed system or ebullated bed, preferably fixed bed, fluidized-bed reactor in existing any form reactor.
Compared with prior art, bromomethane height can be optionally converted into isobutene. by the method that the present invention relates to.Use the halide preparing isobutene catalyst of co-precipitation preparation by the inventive method, by controlling deposition condition and subsequent step, the Disamarium trioxide of addition can be made to realize combining closely of molecular level with alumina support, improve the corrosion resistance of catalyst；Meanwhile, use the method can also improve the dispersion in Zn element and active center, improve the activity of catalyst.The present invention relates to bromomethane conversion preparing isobutene method for preparing catalyst simple, it is easy to industrialization.Bromomethane of the present invention converts preparing isobutene method and has reaction condition gentleness, selectivity of product advantages of higher, easily realizes industrialization, and application prospect is boundless.
Detailed description of the invention
Further illustrate technology contents and the effect of the present invention below in conjunction with embodiment, but be not intended to the present invention.Catalyst acidimetric estimation uses NH3-TPD method, the INSTRUMENT MODEL of employing is MICROMERITICS company of U.S. AutoChem
2920 chemical adsorption instruments, concrete to measure process as follows: sample being cooled to 150 DEG C by helium purge after 1 hour at 450 DEG C, introduces the mixed gas of ammonia and helium, ammonia volume content 10%, Pulse adsorption reaches balance for five times；Helium purge 2 hours, then carries out ammonia with the programming rate temperature programming of 10 DEG C/min and is desorbed to 450 DEG C；Ammonia after desorption uses the detection of TCD detector, quantitative Analysis catalyst surface acid amount.
Embodiment
1
Weigh appropriate zinc nitrate, samaric nitrate, aluminum nitrate is dissolved completely in deionized water, is 1 ~ 3 by nitric acid regulation solution ph；At 40 ~ 80 DEG C, being slowly added dropwise 25 wt% ammonia and be co-precipitated, the pH value controlling mother solution in precipitation process is 8 ~ 11, and the suspension of generation stands aging 6 hours at 70 DEG C；The precipitate of gained, after filtering, washing, is put in baking oven and is dried 24 hours at 80 DEG C, roasting 8 hours at 400 DEG C；Prepare catalyst precarsor ZnO-SmO/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 250 DEG C, 0.1MPa, 100h-1, the time is 2h.Preparing catalyst, its weight consists of ZnBr2Content is 31.2%, and ZnO content is 3.7%, and Sm content in terms of oxide is 5%, and in catalyst, less than 450 DEG C total acid contents are 0.84mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 52.25% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 50%, and reaction temperature is 230 DEG C, and reaction pressure is 1MPa(absolute pressure), air speed is 500h-1, it is passed through unstripped gas procatalyst and activates in a hydrogen atmosphere, reducing condition is 400 DEG C, 0.2MPa(absolute pressure), 1000h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 65.28%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 95.78%, selective isobutene 87.65%.
Embodiment
2
Weigh appropriate zinc nitrate, samaric nitrate, aluminum nitrate is dissolved completely in deionized water, is 1 ~ 3 by nitric acid regulation solution ph；At 40 ~ 80 DEG C, being slowly added dropwise 25 wt% ammonia and be co-precipitated, the pH value controlling mother solution in precipitation process is 8 ~ 11, and the suspension of generation stands aging 8 hours at 80 DEG C；The precipitate of gained, after filtering, washing, is put in baking oven and is dried 16 hours at 100 DEG C, roasting 4 hours at 450 DEG C；Prepare catalyst precarsor ZnO-SmO/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 50%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.2MPa, 200h-1, the time is 4h.Preparing catalyst, its weight consists of ZnBr2Content is 8.7%, and ZnO content is 1.6%, and Sm content in terms of oxide is 5%.In catalyst, less than 450 DEG C total acid contents are 0.6mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 64.01% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 51.7%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 68.69%, selective isobutene 66.92%.
Embodiment
3
Weigh appropriate zinc nitrate, samaric nitrate, aluminum nitrate is dissolved completely in deionized water, is 1 ~ 3 by nitric acid regulation solution ph；At 40 ~ 80 DEG C, being slowly added dropwise 25 wt% ammonia and be co-precipitated, the pH value controlling mother solution in precipitation process is 8 ~ 11, and the suspension of generation stands aging 10 hours at 90 DEG C；The precipitate of gained, after filtering, washing, is put in baking oven and is dried 12 hours at 120 DEG C, roasting 8 hours at 350 DEG C；Prepare catalyst precarsor ZnO-SmO/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 70%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 2h.Preparing catalyst, its weight consists of ZnBr2Content is 17.3%, and ZnO content is 3.1%, and Sm content in terms of oxide is 5%.In catalyst, less than 450 DEG C total acid contents are 0.73mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 59% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 80%, and reaction temperature is 200 DEG C, and reaction pressure is 3MPa(absolute pressure), air speed is 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 50%, and reducing condition is 500 DEG C, 0.1MPa(absolute pressure), 500h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 45.66%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 90.71%, selective isobutene 83.68%.
Embodiment
4
Weigh appropriate zinc nitrate, samaric nitrate, aluminum nitrate is dissolved completely in deionized water, is 1 ~ 3 by nitric acid regulation solution ph；At 40 ~ 80 DEG C, being slowly added dropwise 25 wt% ammonia and be co-precipitated, the pH value controlling mother solution in precipitation process is 8 ~ 11, and the suspension of generation stands aging 6 hours at 80 DEG C；The precipitate of gained, after filtering, washing, is put in baking oven and is dried 12 hours at 120 DEG C, roasting 8 hours at 350 DEG C；Prepare catalyst precarsor ZnO-SmO/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 50%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 2h.Preparing catalyst, its weight consists of ZnBr2Content is 20.8%, and ZnO content is 5.6%, and Sm content in terms of oxide is 2%.In catalyst, less than 450 DEG C total acid contents are 0.81mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 40.31% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 30%, and reaction temperature is 270 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 70%, and reducing condition is 350 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 6h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 55.9%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 85.63%, selective isobutene 72.08%.
Embodiment
5
Weigh appropriate zinc nitrate, samaric nitrate, aluminum nitrate is dissolved completely in deionized water, is 1 ~ 3 by nitric acid regulation solution ph；At 40 ~ 80 DEG C, being slowly added dropwise 25 wt% ammonia and be co-precipitated, the pH value controlling mother solution in precipitation process is 8 ~ 11, and the suspension of generation stands aging 6 hours at 80 DEG C；The precipitate of gained, after filtering, washing, is put in baking oven and is dried 12 hours at 120 DEG C, roasting 8 hours at 350 DEG C；Prepare catalyst precarsor ZnO-SmO/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 50%, and surplus is nitrogen, and treatment conditions are 200 DEG C, 0.1MPa, 100h-1, the time is 4h.Preparing catalyst, its weight consists of ZnBr2Content is 26%, and ZnO content is 4.7%, and Sm content in terms of oxide is 10%.In catalyst, less than 450 DEG C total acid contents are 0.95mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 50.32% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane, and reaction temperature is 270 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 60%, and reducing condition is 550 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 8h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 40%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 94.81%, selective isobutene 84.64%.
Embodiment
6
Weigh appropriate zinc nitrate, samaric nitrate, aluminum nitrate is dissolved completely in deionized water, is 1 ~ 3 by nitric acid regulation solution ph；At 40 ~ 80 DEG C, being slowly added dropwise 25 wt% ammonia and be co-precipitated, the pH value controlling mother solution in precipitation process is 8 ~ 11, and the suspension of generation stands aging 6 hours at 80 DEG C；The precipitate of gained, after filtering, washing, is put in baking oven and is dried 12 hours at 120 DEG C, roasting 8 hours at 350 DEG C；Prepare catalyst precarsor ZnO-SmO/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 30%, and treatment conditions are 250 DEG C, 0.1MPa, 100h-1, the time is 2h.Preparing catalyst, its weight consists of ZnBr2Content is 31.2%, and ZnO content is 3.7%, and Sm content in terms of oxide is 5%.In catalyst, less than 450 DEG C total acid contents are 0.79mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 66.18% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 50%, and reaction temperature is 230 DEG C, and reaction pressure is 0.1MPa(absolute pressure), air speed is 500h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), 1000h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 56.46%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 57.54%, selective isobutene 74.15%.
Embodiment
7
Weigh appropriate zinc nitrate, samaric nitrate, aluminum nitrate is dissolved completely in deionized water, is 1 ~ 3 by nitric acid regulation solution ph；At 40 ~ 80 DEG C, being slowly added dropwise 25 wt% ammonia and be co-precipitated, the pH value controlling mother solution in precipitation process is 8 ~ 11, and the suspension of generation stands aging 6 hours at 80 DEG C；The precipitate of gained, after filtering, washing, is put in baking oven and is dried 12 hours at 120 DEG C, roasting 8 hours at 350 DEG C；Prepare catalyst precarsor ZnO-SmO/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 4h.Preparing catalyst, its weight consists of ZnBr2Content is 15.6%, and ZnO content is 6.5%, and Sm content in terms of oxide is 5%.In catalyst, less than 450 DEG C total acid contents are 0.85mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 60.6% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 60.64%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 72.04%, selective isobutene 69.05%.
Embodiment
8
Weigh appropriate zinc nitrate, samaric nitrate, aluminum nitrate is dissolved completely in deionized water, is 1 ~ 3 by nitric acid regulation solution ph；At 40 ~ 80 DEG C, being slowly added dropwise 25 wt% ammonia and be co-precipitated, the pH value controlling mother solution in precipitation process is 8 ~ 11, and the suspension of generation stands aging 6 hours at 80 DEG C；The precipitate of gained, after filtering, washing, is put in baking oven and is dried 12 hours at 120 DEG C, roasting 8 hours at 350 DEG C；Prepare catalyst precarsor ZnO-SmO/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 4h.Preparing catalyst, its weight consists of ZnBr2Content is 20.8%, and ZnO content is 5.6%, and Smr content in terms of oxide is 5%.In catalyst, less than 450 DEG C total acid contents are 0.82mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 54.58% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 61.62%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 78.95%, selective isobutene 83.68%.
Embodiment
9
Weigh appropriate zinc nitrate, samaric nitrate, aluminum nitrate is dissolved completely in deionized water, is 1 ~ 3 by nitric acid regulation solution ph；At 40 ~ 80 DEG C, being slowly added dropwise 25 wt% ammonia and be co-precipitated, the pH value controlling mother solution in precipitation process is 8 ~ 11, and the suspension of generation stands aging 6 hours at 80 DEG C；The precipitate of gained, after filtering, washing, is put in baking oven and is dried 12 hours at 120 DEG C, roasting 8 hours at 350 DEG C；Prepare catalyst precarsor ZnO-SmO/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 4h.Preparing catalyst, its weight consists of ZnBr2Content is 36.3%, and ZnO content is 2.8%, and Sm content in terms of oxide is 5%.In catalyst, less than 450 DEG C total acid contents are 0.98mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 56.66% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 37.84%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 69.59%, selective isobutene 58.19%.
Embodiment
10
Weigh appropriate zinc nitrate, samaric nitrate, aluminum nitrate is dissolved completely in deionized water, is 1 ~ 3 by nitric acid regulation solution ph；At 40 ~ 80 DEG C, being slowly added dropwise 25 wt% ammonia and be co-precipitated, the pH value controlling mother solution is 8 ~ 11, and the suspension of generation stands aging 6 hours at 80 DEG C；The precipitate of gained, after filtering, washing, is put in baking oven and is dried 12 hours at 120 DEG C, roasting 8 hours at 350 DEG C；Prepare catalyst precarsor ZnO-SmO/Al2O3.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 4h.Preparing catalyst, its weight consists of ZnBr2Content is 35.9%, and ZnO content is 3.1%, and Sm content in terms of oxide is 5%.In catalyst, less than 450 DEG C total acid contents are 1.03mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 63.42% of less than 450 DEG C total acid contents.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 80%, and reaction temperature is 200 DEG C, and reaction pressure is 3MPa(absolute pressure), air speed is 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 90%, and reducing condition is 500 DEG C, 0.1MPa(absolute pressure), 500h-1, recovery time 6h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 50.22%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 37.44%, selective isobutene 42.08%.
Comparative example
1
Catalyst is prepared with embodiment 5.Evaluating catalyst condition is with embodiment 5, and difference is, does not carries out activation processing.After reacting one hour, sampling analysis.Bromomethane conversion ratio 2.81%, selective isobutene 0.
Comparative example
2
Catalyst is prepared with embodiment 5, and difference is, does not carries out halogenation treatment.Evaluating catalyst condition is with embodiment 5, after reacting one hour, and sampling analysis.Bromomethane conversion ratio 97.54%, selective isobutene 0.
Comparative example
3
Catalyst is prepared with embodiment 5.Evaluating catalyst condition is with embodiment 5, and difference is, is zinc by zinc bromide Restore All.After reacting one hour, sampling analysis.Bromomethane conversion ratio 2.05%, selective isobutene 0.
Claims (20)
1. a rare-earth element modified halide preparing isobutene catalyst, it is characterised in that: in described catalyst, zinc oxide weight content is 0.5%-20%, and zinc halide weight content is 10%-50%, and Disamarium trioxide weight content is 0.1%-20%, and surplus is alumina catalyst support.
Catalyst the most according to claim 1, it is characterised in that: in described catalyst, zinc oxide weight content is 1%-15%；Zinc halide weight content is 15%-45%；Disamarium trioxide weight content is 0.1%-15%.
Catalyst the most according to claim 1, it is characterised in that: in described catalyst, zinc oxide weight content is 1%-9%；Zinc halide weight content is 18%-39%；Disamarium trioxide weight content is 0.5%-10%.
Catalyst the most according to claim 1, it is characterised in that: in catalyst, less than 450 DEG C total acid contents are 0.5mmol/g-1.3mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 20%-90% of less than 450 DEG C total acid contents.
Catalyst the most according to claim 4, it is characterised in that: in catalyst, less than 450 DEG C total acid contents are 0.6mmol/g-1.2mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 30%-80% of less than 450 DEG C total acid contents.
Catalyst the most according to claim 5, it is characterised in that: in catalyst, less than 450 DEG C total acid contents are 0.7mmol-1.1mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 40%-80% of less than 450 DEG C total acid contents.
7. the preparation method of catalyst described in claim 1, it is characterised in that: include following preparation process:
(1) zinc precursor, samarium presoma and support precursor are dissolved in the water it are configured to the solution that pH value is 1 ~ 3；At 40 ~ 80 DEG C, being slowly added dropwise alkaline solution and be co-precipitated, the pH value controlling mother solution in precipitation process is 8 ~ 11；After precipitation terminates, stand aging, then filter, wash, through being dried, catalyst precarsor can be prepared after roasting；
(2) step (1) gained material is carried out halogenation treatment, prepare halide preparing isobutene catalyst.
Method the most according to claim 7, it is characterised in that: in step (1), zinc, samarium, support precursor are nitrate, sulfate or halogenide, preferably nitrate；Described alkaline solution is sodium carbonate, sodium bicarbonate or ammonia, preferably ammonia.
Method the most according to claim 7, it is characterised in that: in step (1), aging temperature is 10 DEG C-90 DEG C, and preferably 70 DEG C-90 DEG C, ageing time is 1h-24h, preferably 6h-10h.
Method the most according to claim 7, it is characterised in that: step (1) includes being dried and roasting process, and baking temperature is 50 DEG C-200 DEG C, preferably 60 DEG C-150 DEG C, more preferably 80 DEG C-120 DEG C；Drying time is 1h-48h, preferably 2h-36h, more preferably 2h-24h；Sintering 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 2h-16h, more preferably 4h-8h.
11. methods according to claim 7, it is characterized in that: described in step (2), halogenation treatment process is as follows: the sample of step (1) is placed in continuous fixed bed reactor, 150 DEG C-400 DEG C it are warming up under inert atmosphere, being passed through halide and noble gas mixtures, in gaseous mixture, halide volumn concentration is 1%-95%；Gas space velocity is 50h-1-1000
h-1；Processing pressure is 0.1MPa-0.5MPa, and the process time is 0.5h-8h.
12. methods according to claim 11, it is characterised in that: being warming up to 180 DEG C-350 DEG C under inert atmosphere, gas space velocity is 100h-1-500h-1；Processing pressure is 0.1MPa-0.3MPa, and the process time is 1h-4h.
The application of catalyst described in 13. claim 1, it is characterised in that: with halide as raw material, reaction temperature is 150 DEG C-350 DEG C；Reaction pressure is 0.1MPa-5MPa；Air speed is 50h-1-1000h-1, needing before charging catalyst is carried out reduction treatment, the content of halogen being reduced in catalyst is the 20%-90% of total halogen content in reduction procatalyst.
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, the content of halogen being reduced in catalyst is the 30%-80% of total halogen content in reduction procatalyst.
15. application according to claim 14, it is characterised in that: reduction treatment process is as follows: by catalyzer temperature-elevating to 300 DEG C-600 DEG C under inert atmosphere；Then passing to air speed is 200h-1-2000h-1Hydrogen or the mixed gas of hydrogen and noble gas, under 0.1MPa-0.5Mpa, process 2h-16h, be down to reaction temperature and be passed through halide and react, in gaseous mixture, hydrogen volume percentage composition is 10%-95%.
16. application according to claim 15, it is characterised in that: by catalyzer temperature-elevating to 350 DEG C-550 DEG C under inert atmosphere；Then passing to air speed is 500h-1-1000h-1Hydrogen or the mixed gas of hydrogen and noble gas, under 0.1MPa-0.3Mpa, process 4h-8h, in described gaseous mixture, hydrogen volume percentage composition is 30%-90%.
17. application according to claim 13, it is characterised in that: raw material is the mixed gas of halide and noble gas, and in mixed gas, the volumetric concentration of halide is 10%-90%, preferably 30%-80%.
18. application according to claim 13, it is characterised in that: noble gas is one or more in nitrogen, argon, helium.
19. application according to claim 13, it is characterised in that: halide raw material is one or more in a halide, methylene halide, three halides.
20. application according to claim 19, it is characterised in that: halide raw material is one or more in a bromomethane, methylene bromide, bromoform.
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