CN106140221A

CN106140221A - A kind of catalyst of support type halide preparing isobutene and preparation method thereof

Info

Publication number: CN106140221A
Application number: CN201510135833.3A
Authority: CN
Inventors: 张信伟; 张舒冬; 李�杰; 孙晓丹; 倪向前; 尹泽群; 刘全杰; 张喜文
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2015-03-27
Filing date: 2015-03-27
Publication date: 2016-11-23
Anticipated expiration: 2035-03-27
Also published as: CN106140221B

Abstract

The open a kind of support type halide preparing isobutene catalyst of the present invention, in described catalyst, zinc oxide weight content is 0.5%-20%, and zinc halide weight content is 10%-50%, and zirconium oxide weight content is 0.1%-20%, yittrium oxide weight content is 0.1%-20%, and surplus is alumina catalyst support.Method for preparing catalyst is: (1) uses co-impregnation to prepare catalyst precarsor；(2) catalyst precarsor of step (1) gained is carried out halogenation treatment, prepare halide preparing isobutene catalyst.This catalyst can prepare isobutene. by high selectivity.

Description

A kind of catalyst of support type halide preparing isobutene and preparation method thereof

Technical field

The present invention relates to a kind of catalyst and preparation method thereof, relate in particular to catalyst of a kind of support type halide height selectivity preparing isobutene 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 discloses 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, it is an object of the present invention to provide a kind of support type halide preparing isobutene catalyst and its preparation method and application.

A kind of support type 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%；Zirconium oxide weight content is 0.1%-20%, preferably 0.1%-15%, more preferably 0.5%-10%；Yittrium oxide weight content is 0.1%-20%, preferably 0.1%-15%, more preferably 0.5%-10%；Surplus is alumina catalyst support.

In described 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 preparation method of above-mentioned catalyst, comprises the steps:

(1) use co-impregnation zinc element presoma, zirconium auxiliary agent presoma and yttrium auxiliary agent presoma to be carried on alumina support, after drying, roasting, prepare catalyst precarsor；

(2) step (1) gained material is carried out halogenation treatment, halide preparing isobutene catalyst can be prepared.

The inventive method, in step (1), described zinc element presoma, zirconium auxiliary agent presoma, yttrium auxiliary agent presoma are nitrate, sulfate, halogenide etc., preferably nitrate.

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) 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, 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.Bromomethane converts the reaction of preparing isobutene, and its product, in addition to isobutene., also generates highly acid hydrogen bromide.In course of reaction, hydrogen bromide can generate aluminium bromide with the aluminium oxide effect on catalyst, and at the reaction temperatures, aluminium bromide can gradually run off, and catalyst structure can be caused destroyed and inactivate.The present invention uses and adds yttrium auxiliary agent, the acid resistance of alumina support can be improved, improve the stability of catalyst.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 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, zirconium nitrate, Yttrium trinitrate are dissolved in deionized water, and (butt, 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) surface, 80 DEG C of dry 12h, 400 DEG C of roasting 8h, prepare catalyst precarsor ZnO-ZrO₂-Y₂O₃/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 15.9%, and ZnO content is 2.9%, and Zr content in terms of oxide is 5.5%, and Y content in terms of oxide is 2.6%.In catalyst, less than 450 DEG C total acid contents are 0.76mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 59.91% 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 87.98%, selective isobutene 81.17%.

Embodiment 2

Weigh appropriate zinc nitrate, zirconium nitrate, Yttrium trinitrate are dissolved in deionized water, and (butt, 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) surface, 100 DEG C of dry 8h, 450 DEG C of roasting 4h, prepare catalyst precarsor ZnO-ZrO₂-Y₂O₃/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 32.8%, and ZnO content is 3.9%, and Zr content in terms of oxide is 4.9%, and Y content in terms of oxide is 2.1%.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 51.74% 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 92.91%, selective isobutene 85.02%.

Embodiment 3

Weigh appropriate zinc nitrate, zirconium nitrate, Yttrium trinitrate are dissolved in deionized water, and (butt, 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) surface, 120 DEG C of dry 4h, 350 DEG C of roasting 8h, prepare catalyst precarsor ZnO-ZrO₂-Y₂O₃/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 8.3%, and ZnO content is 1.5%, and Zr content in terms of oxide is 5%, and Y content in terms of oxide is 2.5%.In catalyst, less than 450 DEG C total acid contents are 0.66mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 64.66% 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 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 66.63%, selective isobutene 64.91%.

Embodiment 4

Weigh appropriate zinc nitrate, zirconium nitrate, Yttrium trinitrate are dissolved in deionized water, and (butt, 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) surface, 120 DEG C of dry 4h, 350 DEG C of roasting 8h, prepare catalyst precarsor ZnO-ZrO₂-Y₂O₃/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 20.6%, and ZnO content is 5.6%, and Zr content in terms of oxide is 2%, and Y content in terms of oxide is 1.9%.In catalyst, less than 450 DEG C total acid contents are 0.87mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 40.11% 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 83.06%, selective isobutene 69.92%.

Embodiment 5

Weigh appropriate zinc nitrate, zirconium nitrate, Yttrium trinitrate are dissolved in deionized water, and (butt, 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) surface, 120 DEG C of dry 4h, 350 DEG C of roasting 8h, prepare catalyst precarsor ZnO-ZrO₂-Y₂O₃/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 Zr content in terms of oxide is 10.2%, and Y content in terms of oxide is 2.2%.In catalyst, less than 450 DEG C total acid contents are 0.97mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 59.63% 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 91.97%, selective isobutene 82.10%.

Embodiment 6

Weigh appropriate zinc nitrate, zirconium nitrate, Yttrium trinitrate are dissolved in deionized water, and (butt, 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) surface, 120 DEG C of dry 4h, 350 DEG C of roasting 8h, prepare catalyst precarsor ZnO-ZrO₂-Y₂O₃/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 31.6%, and ZnO content is 3.8%, and Zr content in terms of oxide is 5.4%, and Y content in terms of oxide is 0.4%.In catalyst, less than 450 DEG C total acid contents are 0.91mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 67.93% 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 55.81%, selective isobutene 71.93%.

Embodiment 7

Weigh appropriate zinc nitrate, zirconium nitrate, Yttrium trinitrate are dissolved in deionized water, and (butt, 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) surface, 120 DEG C of dry 4h, 350 DEG C of roasting 8h, prepare catalyst precarsor ZnO-ZrO₂-Y₂O₃/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 20.1%, and ZnO content is 5.4%, and Zr content in terms of oxide is 4.9%, and Y content in terms of oxide is 7.6%.In catalyst, less than 450 DEG C total acid contents are 0.86mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 61.22% 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 69.88%, selective isobutene 66.79%.

Embodiment 8

Weigh appropriate zinc nitrate, zirconium nitrate, Yttrium trinitrate are dissolved in deionized water, and (butt, 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) surface, 120 DEG C of dry 4h, 350 DEG C of roasting 8h, prepare catalyst precarsor ZnO-ZrO₂-Y₂O₃/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 1.5h.Preparing catalyst, its weight consists of ZnBr₂Content is 27.3%, and ZnO content is 4.9%, and Zr content in terms of oxide is 4.6%, and Y content in terms of oxide is 2 %.In catalyst, less than 450 DEG C total acid contents are 0.86mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 54.05% 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 76.59%, selective isobutene 81.44%.

Embodiment 9

Weigh appropriate zinc nitrate, zirconium nitrate, Yttrium trinitrate are dissolved in deionized water, and (butt, 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) surface, 120 DEG C of dry 4h, 350 DEG C of roasting 8h, prepare catalyst precarsor ZnO-ZrO₂-Y₂O₃/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 7h.Preparing catalyst, its weight consists of ZnBr₂Content is 29.5%, and ZnO content is 3.5%, and Zr content in terms of oxide is 5.3%, and Y content in terms of oxide is 1.8%.In catalyst, less than 450 DEG C total acid contents are 0.92mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 57.24% 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.Unstripped gas is volume fraction 30% 1 bromomethane and nitrogen mixed gas, and reaction temperature is 230 DEG C, and reaction pressure is normal pressure, and air speed is 200h^-1.Being passed through unstripped gas procatalyst to activate in a hydrogen atmosphere, activation condition is 450 DEG C, 0.1MPa, 500h^-1, the time is 4h.Reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 39.84%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 67.50%, selective isobutene 56.44%.

Embodiment 10

Weigh appropriate zinc nitrate, zirconium nitrate, Yttrium trinitrate are dissolved in deionized water, and (butt, 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) surface, 120 DEG C of dry 4h, 350 DEG C of roasting 8h, prepare catalyst precarsor ZnO-ZrO₂-Y₂O₃/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 280 DEG C, 0.1MPa, 100h^-1, the time is 4h.Preparing catalyst, its weight consists of ZnBr₂Content is 36.6%, and ZnO content is 2.8%, and Zr content in terms of oxide is 5.2%, and Y content in terms of oxide is 2.3%.In catalyst, less than 450 DEG C total acid contents are 1.04mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 62.49% 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.Unstripped gas is volume fraction 30% 1 bromomethane and nitrogen mixed gas, and reaction temperature is 230 DEG C, and reaction pressure is normal pressure, and air speed is 200h^-1.Being passed through unstripped gas procatalyst to activate under hydrogen mixed gas atmosphere, in hydrogen gas mixture, hydrogen volume content is 80%, and surplus is nitrogen, and activation condition is 450 DEG C, 0.1MPa, 500h^-1, the time is 4h.Reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 47.84%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 36.32%, selective isobutene 40.82%.

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 2.85%, 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 98.56%, 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 3.05%, selective isobutene 0.

Claims

1. a support type halide preparing isobutene catalyst, it is characterized in that: in described catalyst, zinc oxide weight content is 0.5%-20%, zinc halide weight content is 10%-50%, and zirconium oxide weight content is 0.1%-20%, yittrium oxide 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%, and zinc halide weight content is 15%-45%, and zirconium oxide weight content is 0.1%-15%, and yittrium oxide 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%, and zinc halide weight content is 18%-39%, and zirconium oxide weight content is 0.5%-10%, and yittrium oxide 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 characterized in that: include following process: (1) uses co-impregnation zinc element presoma, zirconium auxiliary agent presoma and yttrium auxiliary agent presoma to be carried on alumina support, after drying, roasting, prepare catalyst precarsor；(2) step (1) gained material is carried out halogenation treatment, halide preparing isobutene catalyst can be prepared.

Method the most according to claim 7, it is characterised in that: zinc element presoma described in step (1), zirconium auxiliary agent presoma and yttrium auxiliary agent presoma are its inorganic salt or organic salt, preferably nitrate, chlorate, acetate, more preferably nitrate.

Method the most according to claim 8, it is characterised in that: inorganic salt is one or more in nitrate, chlorate, acetate.

Method the most according to claim 7, it is characterised in that: described in step (1), 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-12h.

11. methods according to claim 7, it is characterised in that: described in step (1), 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.

12. methods according to claim 7, it is characterized in that: halogenation process is as follows: the sample of step (1) 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.

13. methods according to claim 12, 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.

The application of catalyst described in 14. 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.

15. application according to claim 14, 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.

16. 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, 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%.

17. application according to claim 16, 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%.

18. application according to claim 14, 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%.

19. application according to claim 18, it is characterised in that: halide raw material is one or more in a halide, methylene halide, three halides, one or more in preferably one bromomethane, methylene bromide, bromoform.

20. application according to claim 14, it is characterised in that: the reaction of halide preparing isobutene is carried out in fixed bed, fluid bed, fixed fluidized bed, moving bed, slurry bed system or fluidized bed reactor.