CN106140215A - A kind of halide preparing isobutene catalyst and its preparation method and application - Google Patents

Abstract

Open a kind of halide preparing isobutene catalyst of the present invention and its preparation method and application.Described catalyst is in terms of weight content, manganese oxide content is 0.5%-20%, preferably 1%-15%, further preferably 1%-10%, manganese halide content is 10%-50%, preferably 15%-45%, further preferably 17%-38%, surplus is carrier, and described manganese halide includes one or more in chloride, bromide, preferably bromide, described carrier is one or more in aluminium oxide, silicon oxide, molecular sieve etc., preferential oxidation aluminum, the preparation method of catalyst is as follows: manganese oxide and/or auxiliary agent oxide are introduced to carrier, and the carrier after introducing manganese oxide is carried out halogenation treatment.This catalyst can prepare high selective isobutene..

Description

A kind of halide preparing isobutene catalyst and its preparation method and application

Technical field

The present invention relates to a kind of halide preparing isobutene catalyst and its preparation method and application, relate in particular to a kind of halide height selectivity preparing isobutene catalyst and its preparation method and application.

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 He, Ting such as Wang Ye 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 halide height and selectively produce isobutene catalyst and its preparation method and application.

A kind of halide preparing isobutene catalyst, based on the weight content of catalyst, manganese oxide content is 0.5%-20%, preferably 1%-15%, further preferred 1%-10%, and manganese halide content is 10%-50%, preferably 15%-45%, further preferred 17%-38%, and surplus is carrier.Described manganese halide includes that one or more in manganese chloride, Manganese dibromide., preferably Manganese dibromide., described carrier are one or more in aluminium oxide, silicon oxide, ZSM-5 molecular sieve etc., preferential oxidation aluminum.

In above-mentioned halide preparing isobutene catalyst, it is also possible to containing appropriate auxiliary agent, one or more in Ti, Zr, Ce, La of described auxiliary agent, preferably zirconium, auxiliary agent counts weight content in the catalyst as 0.1%-10% with element, preferably 0.5%-5%, more preferably 0.5%-3%.

In above-mentioned halide preparing isobutene catalyst, 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 preferred 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%.

The preparation method of above-mentioned halide preparing isobutene catalyst, including following process: manganese oxide and/or auxiliary agent oxide are introduced to carrier, carries out halogenation treatment to the carrier after introducing manganese oxide.

Manganese oxide described in said method and/or auxiliary agent oxide are 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 employ impregnation method to introduce, concrete grammar is as follows: use the carrier after manganese salt, promoter metal salt solution impregnation molding, halogenation treatment is carried out after carrying out halogenation treatment after drying, roasting or first using the carrier drying after manganese salt solution dip forming, roasting, last impregnation aids metal salt solution the most again, is dried, prepares halide preparing isobutene catalyst after roasting.

In said method, manganese salt can be inorganic salt, it is also possible to for one or more in organic salt, preferably nitrate, hydrochlorate, acetate.

In said method, 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 said method, 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.

Halogenation treatment in said method, refers to use gas phase halogen contained compound to process the sample of load manganese oxide.Halogen contained compound refers to one or more in a halide, methylene halide, three halides, preferably one halide, more preferably one bromomethane.Gas phase halogen contained compound can also be used to carry out halogenation treatment with the mixed gas of noble gas, and when using mixed gas halogenation treatment, halide volumetric concentration is not less than 20%, preferably not less than 30%.Concrete halogenation process is as follows: be placed in continuous fixed bed reactor by the sample of load manganese 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.

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(absolute pressure), preferably 0.1MPa-3MPa(absolute pressure)；Air speed is 50h^-1-1000h^-1, preferably 200h^-1-500h^-1, needing catalyst is carried out activation processing before charging, the content of halogen activated to 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 activated 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, in 0.1MPa-0.5MPa(absolute pressure), preferably 0.1MPa-0.3MPa(absolute pressure) process 2h-16h, preferably 4h-8h after, 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.Carry out bromomethane by the inventive method and convert preparing isobutene reaction, bromomethane conversion ratio more than 90%, selective isobutene more than 80%.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 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 manganese 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 MnO₂/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.Catalyst weight consists of: MnBr₂Weight content is 27.1%, MnO₂Weight content is 6.3%, and in catalyst, less than 450 DEG C total acid contents are 0.85 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 57.8% 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 62.02%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 95.9%, selective isobutene 77.9%.

Embodiment 2

Weighing appropriate manganese 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 MnO₂/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 80%, and treatment conditions are 250 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 2h, prepare halide preparing isobutene catalyst.Catalyst weight consists of: MnBr₂Weight content is 30.2%, MnO₂Weight content is 4.2%, and in catalyst, less than 450 DEG C total acid contents are 0.89 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 61.7% 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 49.12%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 97.7%, selective isobutene 82.3%.

Embodiment 3

Weighing appropriate manganese 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 MnO₂/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.Catalyst weight consists of: MnBr₂Weight content is 33.2%, MnO₂Weight content is 2.1%, and in catalyst, less than 450 DEG C total acid contents are 0.90 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 67.6% 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 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 43.38%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 96.2%, selective isobutene 86.1%.

Embodiment 4

Weighing appropriate manganese 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 MnO₂/Al₂O₃.Being placed in continuous fixed bed reactor by 5g catalyst precarsor, use a bromomethane to process catalyst precarsor, treatment conditions are 200 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 1h, prepare halide preparing isobutene catalyst.Catalyst weight consists of: MnBr₂Weight content is 18.1%, MnO₂Weight content is 2.1%, and in catalyst, less than 450 DEG C total acid contents are 0.78 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 63.4% 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 53.11%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 97.3%, selective isobutene 90.0%.

Embodiment 5

Weighing appropriate manganese 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 dry 6h, 500 DEG C of lower roasting 6h of nitrogen protection, prepare catalyst precarsor MnO₂/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 70%, and treatment conditions are 200 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 2h, prepare halide preparing isobutene catalyst.Catalyst weight consists of: MnBr₂Weight content is 39.2%, MnO₂In terms of oxide, weight content is 6.3%, and in catalyst, less than 450 DEG C total acid contents are 0.92 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 62.1% 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 38%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 96.0%, selective isobutene 82.4%.

Embodiment 6

Weighing appropriate manganese 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, it is dried 4h, roasting 4h under 500 DEG C of nitrogen atmospheres under 120 DEG C of nitrogen atmospheres, prepares catalyst precarsor MnO₂/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 1h.Catalyst weight consists of: MnBr₂Weight content is 35.2%, MnO₂Weight content is 9.4%, and in catalyst, less than 450 DEG C total acid contents are 0.88 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 58.8% 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 53.64%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 97.0%, selective isobutene 82.8%.

Embodiment 7

Weighing appropriate manganese 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 4h, prepare catalyst precarsor MnO₂/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 90%, and treatment conditions are 300 DEG C, 0.1MPa(absolute pressure), 500h^-1, time 4h, prepare halide preparing isobutene catalyst.Catalyst weight consists of: MnBr₂Weight content is 20.1%, MnO₂Weight content is 1.1%, and in catalyst, less than 450 DEG C total acid contents are 0.85 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 67.3% 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 47.71%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 95.6%, selective isobutene 83.5%.

Embodiment 8

Weigh appropriate manganese nitrate, zirconium nitrate is dissolved in deionized water, and (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 4h, prepare catalyst precarsor MnO₂-Zr/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 80%, and treatment conditions are 250 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 2h, prepare halide preparing isobutene catalyst.Catalyst weight consists of: MnBr₂Weight content is 30.2%, MnO₂Weight content is 4.2%, and Zr weight content in terms of element is 2.5%, and in catalyst, less than 450 DEG C total acid contents are 1.01 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 64.8% 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 35.95%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 94.3%, selective isobutene 83.9%.

Embodiment 9

Weigh appropriate manganese nitrate, cerous nitrate is dissolved in deionized water, and (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 4h, prepare catalyst precarsor MnO₂-Ce/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 80%, and treatment conditions are 250 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 2h, prepare halide preparing isobutene catalyst.Catalyst weight consists of: MnBr₂Weight content is 30.2%, MnO₂Weight content is 4.2%, and Ce weight content in terms of element is 1.4%, and in catalyst, less than 450 DEG C total acid contents are 0.87 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 64.4% 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 58.54%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 94.8%, selective isobutene 84.5%.

Embodiment 10

Weigh appropriate manganese nitrate, Lanthanum (III) nitrate is dissolved in deionized water, and (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 4h, prepare catalyst precarsor MnO₂-La/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 80%, and treatment conditions are 250 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 2h, prepare halide preparing isobutene catalyst.Catalyst weight consists of: MnBr₂Weight content is 30.2%, MnO₂Weight content is 4.2%, and La weight content in terms of element is 0.9%, and in catalyst, less than 450 DEG C total acid contents are 0.89 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 62.7% 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 57.61%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 97.7%, selective isobutene 85.8%.

Embodiment 11

Weigh appropriate manganese nitrate, Titanium Nitrate is dissolved in deionized water, and (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 4h, prepare catalyst precarsor MnO₂-Ti/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 80%, and treatment conditions are 250 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 2h, prepare halide preparing isobutene catalyst.Catalyst weight consists of: MnBr₂Weight content is 30.2%, MnO₂Weight content is 4.2%, and Ti weight content in terms of element is 3.5%, and in catalyst, less than 450 DEG C total acid contents are 0.91 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 61.8% 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 49.26%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 96.3%, selective isobutene 85.5%.

Embodiment 12

Weighing appropriate manganese chloride 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 4h, prepare catalyst precarsor MnO₂/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 80%, and treatment conditions are 250 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 2h, prepare halide preparing isobutene catalyst.Catalyst weight consists of: MnBr₂Weight content is 30.2%, MnO₂Weight content is 4.2%, and in catalyst, less than 450 DEG C total acid contents are 0.83 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 62.9% 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 43.99%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 97.2%, selective isobutene 85.3%.

Embodiment 13

Weighing appropriate manganese nitrate to be dissolved in deionized water, (pore volume is 1.06ml/g, and specific surface area is 387m to use equi-volume impregnating to be carried on silicon dioxide²/ g, spherical, equivalent diameter 0.5mm) carrier, 120 DEG C of dry 4h, 500 DEG C of roasting 4h, prepare catalyst precarsor MnO₂/SiO₂.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 80%, and treatment conditions are 250 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 2h, prepare halide preparing isobutene catalyst.Catalyst weight consists of: MnBr₂Weight content is 30.2%, MnO₂Weight content is 4.2%, and in catalyst, less than 450 DEG C total acid contents are 1.05 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 55.2% 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 400 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 28.73%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 65.5%, selective isobutene 73.9%.

Embodiment 14

Weighing appropriate manganese nitrate to be dissolved in deionized water, use equi-volume impregnating to be carried on Hydrogen ZSM-5(silica alumina ratio 50, pore volume is 0.23ml/g, and specific surface area is 426m²/ g, bar shaped, equivalent diameter 1.5mm) carrier, 120 DEG C of dry 4h, 500 DEG C of roasting 4h, prepare catalyst precarsor MnO₂/H-ZSM-5.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 80%, and treatment conditions are 250 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 2h, prepare halide preparing isobutene catalyst.Catalyst weight consists of: MnBr₂Weight content is 30.2%, MnO₂Weight content is 4.2%, and in catalyst, less than 450 DEG C total acid contents are 0.97 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 54.7% 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 400 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 73.24%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 95.2%, selective isobutene 59.3%.

Embodiment 15

Weighing appropriate manganese 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 4h, prepare catalyst precarsor MnO₂/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 80%, and treatment conditions are 250 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 2h.Weigh appropriate zirconium nitrate to be dissolved in deionized water, use the sample after equi-volume impregnating dipping bromination, be dried 4h, roasting 4h under 500 DEG C of nitrogen atmospheres under 120 DEG C of nitrogen atmospheres, prepare halide preparing isobutene catalyst.Catalyst weight consists of: MnBr₂Weight content is 30.2%, MnO₂Weight content is 4.2%, and Zr weight content in terms of element is 0.5%, and in catalyst, less than 450 DEG C total acid contents are 0.75 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 65.6% 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 39.1%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 97%, selective isobutene 80.1%.

Embodiment 16

Weighing appropriate manganese 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 4h, prepare catalyst precarsor MnO₂/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 80%, and treatment conditions are 250 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 2h.Weigh appropriate cerous nitrate to be dissolved in deionized water, use the sample after equi-volume impregnating dipping bromination, be dried 8h, roasting 4h under 500 DEG C of nitrogen atmospheres under 80 DEG C of nitrogen atmospheres, prepare halide preparing isobutene catalyst.Catalyst weight consists of: MnBr₂Weight content is 30.2%, MnO₂Weight content is 4.2%, and Ce weight content in terms of element is 0.3%, and in catalyst, less than 450 DEG C total acid contents are 0.79 mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 64.6% 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), 500h^-1, recovery time 6h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 60.15%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 94.3%, selective isobutene 87.8%.

Comparative example 1

Catalyst is prepared with embodiment 2.Evaluating catalyst condition is with embodiment 2, and difference is, does not carries out activation processing.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 3.9%, selective isobutene 0.

Comparative example 2

Catalyst is prepared with embodiment 2, and difference is, does not carries out halogenation treatment.Evaluating catalyst condition is with embodiment 2, and stable reaction is after one hour, sampling analysis.Bromomethane conversion ratio 96.8%, selective isobutene 0.

Comparative example 3

Catalyst is prepared with embodiment 2.Evaluating catalyst condition is with embodiment 2, and difference is, is zinc by zinc bromide Restore All.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 0.6%, selective isobutene 0.

Claims (29)

1. a halide preparing isobutene catalyst, it is characterized in that: based on the weight content of catalyst, manganese oxide content is 0.5%-20%, manganese halide content is 10%-50%, surplus is carrier, described manganese halide includes that one or more in manganese chloride, Manganese dibromide., described carrier are one or more in aluminium oxide, silicon oxide, ZSM-5 molecular sieve.

Catalyst the most according to claim 1, it is characterised in that: manganese oxide content is 1%-15%, and manganese halide content is 15%-45%, and surplus is carrier, and described manganese halide is Manganese dibromide., and described carrier is aluminium oxide.

Catalyst the most according to claim 1, it is characterised in that: manganese oxide content is 1%-10%, and manganese halide content is 17%-38%, and surplus is carrier.

Catalyst the most according to claim 1, it is characterised in that: containing auxiliary agent in catalyst, one or more in Ti, Zr, Ce, La of auxiliary agent, auxiliary agent counts weight content in the catalyst as 0.1%-10% with element.

5. according to the catalyst described in claim 1 or 4, it is characterised in that: auxiliary agent is zirconium, and auxiliary agent counts weight content in the catalyst as 0.5%-5% with element.

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 6, 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 7, 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.

9. the preparation method of the described catalyst of one of claim 1-8, it is characterised in that: include following process: manganese oxide and/or auxiliary agent oxide are introduced to carrier, the carrier after introducing manganese oxide is carried out halogenation treatment.

Method the most according to claim 9, it is characterised in that: described manganese oxide and/or auxiliary agent oxide are introduced to the method for carrier and use impregnation method to introduce, or introduce by the way of kneading when molding, or introduce in carrier material preparation process.

11. methods according to claim 10, it is characterized in that: use impregnation method to introduce, concrete grammar is as follows: use the carrier after manganese salt, promoter metal salt solution impregnation molding, halogenation treatment is carried out after carrying out halogenation treatment after drying, roasting or first using the carrier drying after manganese salt solution dip forming, roasting, last impregnation aids metal salt solution the most again, is dried, prepares halide preparing isobutene catalyst after roasting.

12. methods according to claim 11, it is characterised in that: manganese salt is one or more in nitrate, hydrochlorate, acetate.

13. methods according to claim 11, it is characterised in that: support shapes is bar shaped, sheet shape, cylindricality or spherical.

14. methods according to claim 11, it is characterised in that: baking temperature is 50 DEG C-200 DEG C,；Drying time is 1h-24h；Sintering temperature is 200 DEG C-800 DEG C；Roasting time is 1h-24h.

15. methods according to claim 14, it is characterised in that: baking temperature is 60 DEG C-150 DEG C,；Drying time is 4h-8h；Sintering temperature is 400 DEG C-600 DEG C；Roasting time is 4h-8h.

16. methods according to claim 9, it is characterised in that: halogenation treatment uses gas phase halogen contained compound to process the sample of load manganese oxide.

17. methods according to claim 16, it is characterised in that: halogen contained compound is one or more in a halide, methylene halide, three halides.

18. methods according to claim 16, it is characterised in that: using gas phase halogen contained compound to carry out halogenation treatment with the mixed gas of noble gas, halide volumetric concentration is not less than 20%.

19. methods according to claim 9, it is characterized in that: halogenation process is as follows: the sample of load manganese oxide is placed in continuous fixed bed reactor, being warming up to 150 DEG C-400 DEG C under inert atmosphere, be passed through gas phase halogen contained compound gas, gas space velocity is 50h^-1-1000 h^-1；Carrying out at normal pressure or under the conditions of pressure is 0.1MPa-0.5MPa during process, the process time is 0.5h-8h.

20. methods according to claim 19, 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(absolute pressure), the process time is 1h-4h.

The application in preparing isobutene of one of 21. claim 1 to 8 described catalyst, 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 catalyst is carried out activation processing before charging, the content of halogen activated to catalyst is the 20%-90% of total halogen content in reduction procatalyst.

22. application according to claim 21, 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.

23. application according to claim 21, it is characterised in that: activated 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, process 2h-16h at 0.1MPa-0.5MPa, be down to reaction temperature and be passed through halide and react, in gaseous mixture, hydrogen volume percentage composition is 10%-95%.

24. application according to claim 23, it is characterised in that: it is warming up to 350 DEG C-550 DEG C；Then passing to air speed is 500h^-1-1000h^-1Hydrogen or the mixed gas of hydrogen and noble gas, process 4h-8h at 0.1MPa-0.3Mpa, in described gaseous mixture, hydrogen volume percentage composition is 30%-90%.

25. application according to claim 21, 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%.

26. application according to claim 25, it is characterised in that: noble gas is one or more in nitrogen, argon, helium.

27. application according to claim 21, it is characterised in that: halide raw material is a halide, methylene halide, three halides.

28. application according to claim 21, it is characterised in that: halide raw material is one or more in a bromomethane, methylene bromide, bromoform.

29. application according to claim 22, it is characterised in that: halide preparing isobutene reacts at fixed bed, fluid bed, fixed fluidized bed, moving bed, carries out in slurry bed system or fluidized bed reactor.