CN106146240A - A kind of method of bromomethane preparing isobutene - Google Patents
A kind of method of bromomethane preparing isobutene Download PDFInfo
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Abstract
The present invention discloses a kind of method of bromomethane preparing isobutene, including following content: bromomethane preparing isobutene catalyst first passes around K cryogenic treatment under steam-laden mixed atmosphere, mixed atmosphere through hydrogen activates the most again, the 30%-80% of bromine content during bromine content is activation procatalyst in activation rear catalyst, catalyst after activation contacts acquisition isobutene. with halogenated alkane, described bromomethane preparing isobutene catalyst, based on the weight content of catalyst, zinc oxide content is 0.5%-20%, zinc bromide content is 10%-50%, vector contg 40%-90%, described carrier is aluminium oxide, silicon oxide, one or more in ZSM-5 molecular sieve etc..The method can selectively produce isobutene. by height.
Description
Technical field
A kind of method that the present invention relates to bromomethane preparing isobutene, a kind of method relating in particular to bromomethane height selectivity preparing isobutene.
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, under the overall background that shale gas develops, if it is possible to realize producing isobutene. from methane, a new approach will be provided for obtaining isobutene..But methane stable in properties, the most easily-activated, become the bottleneck of methane chemical utilization.The most many researcheres carry out methane activation, Study on Transformation, among these, the technology that methane converts after halogen functional groupization more one after another, are expected to become the important breakthrough mouth solving a methane transformation technology difficult problem.
Can the many chemical products of preparation from halide.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.
It is mainly methanol, dimethyl ether, acetic acid, higher hydrocarbons, ethylene and propylene etc. currently, with respect to purpose product in the existing document that halide converts.In the technology with the low-carbon alkene of relatively high added value as target product, single selectivity of product is the highest, not yet finds the relevant report of bromomethane high selectivity isobutene..
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method that bromomethane converts preparing isobutene, the method can selectively produce isobutene. by height.
nullThe method of bromomethane preparing isobutene of the present invention includes following content: bromomethane preparing isobutene catalyst first passes around K cryogenic treatment under steam-laden mixed atmosphere，Mixed atmosphere through hydrogen activates the most again，The 30%-80% of bromine content during bromine content is activation procatalyst in activation rear catalyst，It is preferably 40%-60%，Catalyst after activation contacts acquisition isobutene. with halogenated alkane，Described bromomethane preparing isobutene catalyst，Based on the weight content of catalyst，Zinc oxide content is 0.5%-20%，Preferably 1%-15%，Further preferably 1%-9%，Zinc bromide content is 10%-50%，Preferably 15%-45%，Further preferably 18%-39%，Vector contg 40%-90%，Preferably 50%-85%，Further preferably 55%-80%，Described carrier is aluminium oxide、Silicon oxide、One or more in ZSM-5 molecular sieve etc.，Preferential oxidation aluminum.
In said method, bromomethane preparing isobutene catalyst has the feature that less than 450 DEG C total acid contents (NH3-TPD) are 0.5mmol/g-1.3mmol/g, preferably 0.6mmol/g-1.2mmol/g, further 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%, further preferred 40%-80%.
In said method, under the mixed atmosphere of steam, the mixed atmosphere activation detailed process of K cryogenic treatment and hydrogen is as follows: by catalyzer temperature-elevating to 100 DEG C-300 DEG C under inert atmosphere, preferably 150 DEG C-250 DEG C；Then passing to air speed is 100h-1-1000h-1, preferably 300h-1-500h-1The mixed gas of steam and noble gas, in 0.1MPa-0.5MPa(absolute pressure), preferably 0.1MPa-0.3MPa(absolute pressure) process 0.1h-2h, preferably 0.5h-1h after, switch to noble gas.The most under an inert atmosphere by catalyzer temperature-elevating to 300 DEG C-600 DEG C, preferably 350 DEG C-550 DEG C；Then passing to air speed is 200h-1-2000h-1, preferably 500h-1-1000h-1The mixed gas of hydrogen and noble gas, in 0.1MPa-0.5MPa(absolute pressure) under the conditions of process 2h-16h, preferably 0.1MPa-0.3MPa(absolute pressure) process 4h-8h after, be down to reaction temperature and be passed through raw material and react.Described steam is with the gaseous mixture of noble gas, and steam volumn concentration is 5%-30%, preferably 10%-20%.Described hydrogen is with the gaseous mixture of noble gas, and hydrogen volume percentage composition is 10%-95%, preferably 30%-90%, more preferably 50%-90%.
In said method, described halide can be one or more in one or more in a halide, methylene halide, three halides, preferably bromomethane, methylene bromide, bromoform, more preferably bromomethane.
In said method, 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 said method is the gas that nitrogen, argon, helium etc. do not occur chemical reaction under the conditions of involved in the present invention, preferably nitrogen.
Described in said method, the condition of contact includes that reaction temperature is 150 DEG C-350 DEG C；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 said method, 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.
The preparation method of above-mentioned bromomethane preparing isobutene catalyst, including following process: zinc oxide is introduced to carrier, carries out bromination process to the catalyst precarsor after introducing zinc oxide.
Described in the preparation method of above-mentioned bromomethane preparing isobutene catalyst, zinc oxide is introduced to the method that the method for carrier is well known to those skilled in the art, impregnation method can be used to introduce, can also introduce by the way of kneading when molding, it is also possible to introduce when carrier material preparation process such as plastic, co-precipitation.Preferably employing impregnation method to introduce, concrete grammar is as follows: uses the carrier after zinc solution dip forming, carries out bromination process after drying, roasting, prepares bromomethane preparing isobutene catalyst.
In the preparation method of above-mentioned bromomethane preparing isobutene catalyst, zinc salt can be inorganic salt, it is also possible to for one or more in organic salt, preferably nitrate, hydrochlorate, acetate, citrate.
In the preparation method of above-mentioned bromomethane preparing isobutene catalyst, 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-24h, preferably 4h-8h；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 400 DEG C-600 DEG C；Roasting time is 1h-24h, preferably 4h-8h；It can be roasting under the conditions of inert gas shielding during roasting, it is also possible to roasting in air atmosphere.
In the preparation method of above-mentioned bromomethane preparing isobutene catalyst, carrier can be existing commercial product, it is also possible to prepare by those skilled in the art's well-known process.Suitable particle shape can be made or be chosen to carrier according to the needs used, as made bar shaped, sheet shape, cylindricality, spherical etc..Shaping can be carried out by this area general knowledge.
In the preparation method of above-mentioned bromomethane preparing isobutene catalyst, bromination processes, and refers to use gas phase bromine-containing compound to process the sample of load zinc oxide.Bromine-containing compound refers to one or more in bromomethane, methylene bromide, bromoform, preferably bromomethane.Gas phase bromine-containing compound can also be used to carry out bromination process with the mixed gas of noble gas, and when using mixed gas bromination to process, bromomethane volumetric concentration is not less than 20%, preferably not less than 30%.Concrete bromine process is as follows: be placed in continuous fixed bed reactor by the sample of load zinc oxide, 150 DEG C-400 DEG C it are warming up under inert atmosphere, preferably 180 DEG C-350 DEG C, more preferably 200 DEG C-300 DEG C, being passed through gas phase halogen contained compound gas, gas space velocity is 50h-1-1000
h-1, preferably 100h-1-500h-1；Can carry out at normal pressure during process, it is also possible to carry out under a certain pressure, system pressure is 0.1MPa-0.5MPa(absolute pressure), preferably 0.1MPa-0.3MPa(absolute pressure), the process time is 0.5h-8h, preferably 1h-4h.
Noble gas in the preparation method of above-mentioned bromomethane preparing isobutene catalyst and involved by activation method 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 the activation method of the bromomethane preparing isobutene catalyst that the present invention relates to, use the bromine in steam removing free state zinc bromide, and it is converted into zinc oxide, enhance the interaction between zinc oxide, zinc bromide and carrier, it is thus achieved that higher bromomethane conversion ratio and selective isobutene.After converting preparing isobutene catalyst by the inventive method activation bromomethane, carry out bromomethane and convert preparing isobutene reaction, bromomethane conversion ratio more than 90%, selective isobutene more than 90%.The present invention relates to bromomethane conversion preparing isobutene catalyst activation process simple, and mild condition.
Detailed description of the invention
Further illustrate technology contents and the effect of the present invention below in conjunction with embodiment, but be not so limited the present invention.
In following example and comparative example, 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
Weighing appropriate zinc nitrate to be dissolved in deionized water, (pore volume is 0.71ml/g, and specific surface area is 236m to use equi-volume impregnating to be carried on aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, 120 DEG C of dry 4h, 500 DEG C of roasting 8h, prepare catalyst precarsor ZnO/Al2O3.Being placed in continuous fixed bed reactor by 5g catalyst precarsor, use bromomethane to process catalyst precarsor with the mixed gas of nitrogen, bromomethane volumetric concentration is 80%, and treatment conditions are 250 DEG C, 0.3MPa(absolute pressure), 300h-1, time 2h, prepare halide preparing isobutene catalyst, be designated as C-1.Obtain catalyst weight and consist of ZnBr2In terms of bromide, weight content is 30%, and ZnO weight content in terms of oxide is 4%, and in catalyst, less than 450 DEG C total acid contents are 0.93mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 63.2% of less than 450 DEG C total acid contents.
Embodiment 2
Weighing appropriate zinc nitrate to be dissolved in deionized water, (pore volume is 0.71ml/g, and specific surface area is 236m to use equi-volume impregnating to be carried on aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, 80 DEG C of dry 8h, 600 DEG C of roasting 4h, prepare catalyst precarsor ZnO/Al2O3.Being placed in continuous fixed bed reactor by 5g catalyst precarsor, use a bromomethane to process catalyst precarsor, treatment conditions are 250 DEG C, 0.2MPa(absolute pressure), 100h-1, time 2h, prepare halide preparing isobutene catalyst, be designated as C-2.Catalyst weight consists of ZnBr2Weight content is 39%, and ZnO weight content is 6%, and 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 64.5% of less than 450 DEG C total acid contents.
Embodiment 3
Weighing appropriate zinc nitrate to be dissolved in deionized water, (pore volume is 0.71ml/g, and specific surface area is 236m to use equi-volume impregnating to be carried on aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm) carrier, 100 DEG C of vacuum drying 8h, 400 DEG C of roasting 8h, prepare catalyst precarsor ZnO/Al2O3.Being placed in continuous fixed bed reactor by 5g catalyst precarsor, use a bromomethane to process catalyst precarsor with the mixed gas of nitrogen, monobromo volume percent methane is 30%, and treatment conditions are 300 DEG C, 0.1MPa(absolute pressure), 500h-1, time 4h, prepare halide preparing isobutene catalyst, be designated as C-3.Obtain catalyst weight and consist of ZnBr2In terms of bromide, weight content is 18%, and ZnO weight content in terms of oxide is 2%, and in catalyst, less than 450 DEG C total acid contents are 0.72mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 66.1% of less than 450 DEG C total acid contents.
Embodiment 4
Take 5g bromomethane preparing isobutene catalyst C-1 to be placed in continuous fixed bed reactor, by catalyzer temperature-elevating to 200 DEG C under nitrogen atmosphere；Then passing to air speed is 400h-1The mixed gas of steam and nitrogen, wherein steam volumetric concentration is 15%, in 0.2MPa(absolute pressure) process 45min after, switch to nitrogen, then heat to 450 DEG C, being passed through air speed is 800h-1The mixed gas of hydrogen and nitrogen, wherein hydrogen volume concentration is 70%, in 0.2MPa(absolute pressure) process 6h after, be down to reaction temperature and be passed through bromomethane and react.Activation rear catalyst in bromine content be activation procatalyst in bromine content 52.29%.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 200h-1.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.
Embodiment 5
Take 5g bromomethane preparing isobutene catalyst C-1 to be placed in continuous fixed bed reactor, by catalyzer temperature-elevating to 150 DEG C under nitrogen atmosphere；Then passing to air speed is 300h-1The mixed gas of steam and nitrogen, wherein steam volumetric concentration is 10%, in 0.1MPa(absolute pressure) process 30min after, switch to nitrogen, then heat to 450 DEG C, being passed through air speed is 800h-1The mixed gas of hydrogen and nitrogen, wherein hydrogen volume concentration is 70%, in 0.2MPa(absolute pressure) process 6h after, be down to reaction temperature and be passed through bromomethane and react.Activation rear catalyst in bromine content be activation procatalyst in bromine content 56.4%.
After activation terminates, being down to reaction temperature, be passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 350h-1.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.
Embodiment 6
Take 5g bromomethane preparing isobutene catalyst C-1 to be placed in continuous fixed bed reactor, by catalyzer temperature-elevating to 250 DEG C under nitrogen atmosphere；Then passing to air speed is 500h-1The mixed gas of steam and nitrogen, wherein steam volumetric concentration is 20%, in 0.3MPa(absolute pressure) process 60min after, switch to nitrogen, then heat to 450 DEG C, being passed through air speed is 800h-1The mixed gas of hydrogen and nitrogen, wherein hydrogen volume concentration is 70%, in 0.2MPa(absolute pressure) process 6h after, be down to reaction temperature and be passed through bromomethane and react.Activation rear catalyst in bromine content be activation procatalyst in bromine content 59.23%.
After activation terminates, being down to reaction temperature, be passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 350h-1.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.
Embodiment 7
Take 5g bromomethane preparing isobutene catalyst C-1 to be placed in continuous fixed bed reactor, by catalyzer temperature-elevating to 150 DEG C under nitrogen atmosphere；Then passing to air speed is 500h-1The mixed gas of steam and nitrogen, wherein steam volumetric concentration is 15%, in 0.2MPa(absolute pressure) process 60min after, switch to nitrogen, then heat to 450 DEG C, being passed through air speed is 800h-1The mixed gas of hydrogen and nitrogen, wherein hydrogen volume concentration is 70%, in 0.2MPa(absolute pressure) process 6h after, be down to reaction temperature and be passed through bromomethane and react.Activation rear catalyst in bromine content be activation procatalyst in bromine content 50.91%.
After activation terminates, being down to reaction temperature, be passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 60%, and reaction temperature is 230 DEG C, and reaction pressure is 1MPa(absolute pressure), air speed is 350h-1.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.
Embodiment 8
Take 5g bromomethane preparing isobutene catalyst C-1 to be placed in continuous fixed bed reactor, by catalyzer temperature-elevating to 200 DEG C under nitrogen atmosphere；Then passing to air speed is 400h-1The mixed gas of steam and nitrogen, wherein steam volumetric concentration is 15%, in 0.2MPa(absolute pressure) process 45min after, switch to nitrogen, then heat to 350 DEG C, being passed through air speed is 500h-1The mixed gas of hydrogen and nitrogen, wherein hydrogen volume concentration is 50%, in 0.1MPa(absolute pressure) process 4h after, be down to reaction temperature and be passed through bromomethane and react.Activation rear catalyst in bromine content be activation procatalyst in bromine content 57.41%.
After activation terminates, being down to reaction temperature, be passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 40%, and reaction temperature is 210 DEG C, and reaction pressure is 3MPa(absolute pressure), air speed is 200h-1.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.
Embodiment 9
Take 5g bromomethane preparing isobutene catalyst C-1 to be placed in continuous fixed bed reactor, by catalyzer temperature-elevating to 200 DEG C under nitrogen atmosphere；Then passing to air speed is 400h-1The mixed gas of steam and nitrogen, wherein steam volumetric concentration is 15%, in 0.2MPa(absolute pressure) process 45min after, switch to nitrogen, then heat to 550 DEG C, being passed through air speed is 1000h-1The mixed gas of hydrogen and nitrogen, wherein hydrogen volume concentration is 90%, in 0.3MPa(absolute pressure) process 8h after, be down to reaction temperature and be passed through bromomethane and react.Activation rear catalyst in bromine content be activation procatalyst in bromine content 49.73%.
After activation terminates, being down to reaction temperature, be passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 80%, and reaction temperature is 270 DEG C, and reaction pressure is 0.1MPa(absolute pressure), air speed is 500h-1.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.
Embodiment 10
Take 5g bromomethane preparing isobutene catalyst C-2 to be placed in continuous fixed bed reactor, by catalyzer temperature-elevating to 200 DEG C under nitrogen atmosphere；Then passing to air speed is 400h-1The mixed gas of steam and nitrogen, wherein steam volumetric concentration is 15%, in 0.2MPa(absolute pressure) process 45min after, switch to nitrogen, then heat to 450 DEG C, being passed through air speed is 800h-1The mixed gas of hydrogen and nitrogen, wherein hydrogen volume concentration is 70%, in 0.2MPa(absolute pressure) process 6h after, be down to reaction temperature and be passed through bromomethane and react.Activation rear catalyst in bromine content be activation procatalyst in bromine content 43.24%.
After activation terminates, being down to reaction temperature, be passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 350h-1.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.
Embodiment 11
Take 5g bromomethane preparing isobutene catalyst C-3 to be placed in continuous fixed bed reactor, by catalyzer temperature-elevating to 200 DEG C under nitrogen atmosphere；Then passing to air speed is 400h-1The mixed gas of steam and nitrogen, wherein steam volumetric concentration is 15%, in 0.2MPa(absolute pressure) process 45min after, switch to nitrogen, then heat to 450 DEG C, being passed through air speed is 800h-1The mixed gas of hydrogen and nitrogen, wherein hydrogen volume concentration is 70%, in 0.2MPa(absolute pressure) process 6h after, be down to reaction temperature and be passed through bromomethane and react.Activation rear catalyst in bromine content be activation procatalyst in bromine content 58.09%.
After activation terminates, being down to reaction temperature, be passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 350h-1.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.
Comparative example 1
Catalyst does not carry out debrominate activation, direct reaction.
Take 5g bromomethane preparing isobutene catalyst C-1 to be placed in continuous fixed bed reactor, be passed directly into unstripped gas reaction.Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 350h-1.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.
Comparative example 2
Catalyst uses hydrogen debrominate activation.
Taking 5g bromomethane preparing isobutene catalyst C-1 to be placed in continuous fixed bed reactor, by catalyzer temperature-elevating to 450 DEG C under nitrogen atmosphere, being passed through air speed is 800h-1The mixed gas of hydrogen and nitrogen, wherein hydrogen volume concentration is 70%, in 0.2MPa(absolute pressure) process 6h after, be down to reaction temperature and be passed through bromomethane and react.Activation rear catalyst in bromine content be activation procatalyst in bromine content 54.51%.
After activation terminates, being down to reaction temperature, be passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 350h-1.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.
Table 1 reaction result
Claims (23)
1. the method for bromomethane preparing isobutene, it is characterized in that: include following content: bromomethane preparing isobutene catalyst first passes around K cryogenic treatment under steam-laden mixed atmosphere, mixed atmosphere through hydrogen activates the most again, the 30%-80% of bromine content during bromine content is activation procatalyst in activation rear catalyst, catalyst after activation contacts acquisition isobutene. with halogenated alkane, described bromomethane preparing isobutene catalyst, content meter by weight, zinc oxide content is 0.5%-20%, zinc bromide content is 10%-50%, vector contg 40%-90%, described carrier is aluminium oxide, silicon oxide, one or more in ZSM-5 molecular sieve etc..
Method the most according to claim 1, it is characterized in that: the 40%-60% of bromine content during bromine content is activation procatalyst in activation rear catalyst, described bromomethane preparing isobutene catalyst content meter by weight, zinc oxide content is 1%-15%, zinc bromide content is 15%-45%, vector contg 50%-85%, described carrier is aluminium oxide.
Method the most according to claim 2, it is characterised in that: zinc oxide content is 1%-9%, and zinc bromide content is 18%-39%, vector contg 55%-80%.
Method the most according to claim 1, it is characterised in that: in bromomethane preparing isobutene 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.
Method the most according to claim 1, it is characterised in that: under steam mixed atmosphere, the mixed atmosphere activation process of K cryogenic treatment and hydrogen is as follows: by catalyzer temperature-elevating to 100 DEG C-300 DEG C under inert atmosphere, and then passing to air speed is 100h-1-1000h-1The mixed gas of steam and noble gas, after 0.1MPa-0.5MPa processes 0.1h-2h, switch to noble gas, it is 200h that catalyzer temperature-elevating to 300 DEG C-600 DEG C then passes to air speed under an inert atmosphere-1-2000h-1The mixed gas of hydrogen and noble gas, after 0.1MPa-0.5MPa processes 2h-16h, it is down to reaction temperature be passed through raw material and react, in the gaseous mixture of described steam and noble gas, steam volumn concentration is 5%-30%, described hydrogen is with the gaseous mixture of noble gas, and hydrogen volume percentage composition is 10%-95%.
Method the most according to claim 5, it is characterised in that: by catalyzer temperature-elevating to 150 DEG C-250 DEG C under inert atmosphere；Then passing to air speed is 300h-1-500h-1The mixed gas of steam and noble gas, after 0.1MPa-0.3MPa processes 0.5h-1h, switch to noble gas, under an inert atmosphere by catalyzer temperature-elevating to 350 DEG C-550 DEG C；Then passing to air speed is 500h-1-1000h-1The mixed gas of hydrogen and noble gas, after 0.1MPa-0.3MPa processes 4h-8h, it is down to reaction temperature be passed through raw material and react, in the gaseous mixture of described steam and noble gas, steam volumn concentration is 10%-20%, described hydrogen is with the gaseous mixture of noble gas, and hydrogen volume percentage composition is, 30%-90%.
Method the most according to claim 1, it is characterised in that: halide is one or more in a halide, methylene halide, three halides.
Method the most according to claim 7, it is characterised in that: halide is one or more in bromomethane, methylene bromide, bromoform.
Method the most according to claim 1, 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%.
Method the most according to claim 9, it is characterised in that: noble gas is nitrogen, argon or helium.
Method the most according to claim 1, it is characterised in that: the condition of contact includes that reaction temperature is 150 DEG C-350 DEG C；Reaction pressure is 0.1MPa-5MPa；Air speed is 50h-1-1000h-1。
12. methods according to claim 11, 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。
13. methods according to claim 1, it is characterised in that: reaction is carried out in fixed bed, fluid bed, fixed fluidized bed, moving bed, slurry bed system or fluidized bed reactor.
14. methods according to claim 1, it is characterised in that: the preparation method of bromomethane preparing isobutene catalyst, including following process: zinc oxide is introduced to carrier, the catalyst precarsor after introducing zinc oxide is carried out bromination process.
15. methods according to claim 14, it is characterised in that: zinc oxide is introduced to the method for carrier and uses impregnation method or the mode of kneading or introduce when carrier material preparation process.
16. methods according to claim 14, it is characterised in that: use the carrier after zinc solution dip forming, after drying, roasting, carry out bromination process, prepare bromomethane preparing isobutene catalyst.
17. methods according to claim 16, it is characterised in that: zinc salt is one or more in nitrate, hydrochlorate, acetate, citrate.
18. methods according to claim 16, it is characterised in that: baking temperature is 50 DEG C-200 DEG C, and drying time is 1h-24h, and sintering temperature is 200 DEG C-800 DEG C, and roasting time is 1h-24h.
19. methods according to claim 14, it is characterised in that: bromination processes and refers to use gas phase bromine-containing compound to process the sample of load zinc oxide.
20. methods according to claim 19, it is characterised in that: bromine-containing compound refers to one or more in bromomethane, methylene bromide, bromoform.
21. methods according to claim 19, it is characterised in that: using gas phase bromine-containing compound to carry out bromination process with the mixed gas of noble gas, bromomethane volumetric concentration is not less than 20%.
22. methods according to claim 19, it is characterised in that: being placed in continuous fixed bed reactor by the sample of load zinc oxide, be warming up to 150 DEG C-400 DEG C, be passed through gas phase halogen contained compound gas under inert atmosphere, gas space velocity is 50h-1-1000
h-1；System pressure is 0.1MPa-0.5MPa, and the process time is 0.5h-8h.
23. methods according to claim 22, 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；System pressure is 0.1MPa-0.3MPa, and the process time is 1h-4h.
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| CN102527427A (en) * | 2012-01-06 | 2012-07-04 | 厦门大学 | Modified molecular sieve catalyst for preparing propylene by methinehalide and preparation method of modified molecular sieve catalyst |
| CN104211556A (en) * | 2013-06-05 | 2014-12-17 | 中国石油化工股份有限公司 | Preparation method for low carbon olefin |
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| JPH04103541A (en) * | 1990-08-24 | 1992-04-06 | Tosoh Corp | Production of olefin |
| US6486368B1 (en) * | 2001-06-20 | 2002-11-26 | Grt, Inc. | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes |
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| CN102527427A (en) * | 2012-01-06 | 2012-07-04 | 厦门大学 | Modified molecular sieve catalyst for preparing propylene by methinehalide and preparation method of modified molecular sieve catalyst |
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