CN106140212A - A kind of preparing isobutene catalyst and preparation method thereof - Google Patents

Abstract

Open a kind of preparing isobutene catalyst of the present invention and preparation method thereof, catalyst is prepared and is included following process: (1) zinc supported element on the alumina support and auxiliary agent zr element presoma, prepares catalyst precarsor after drying, roasting；(2) step (1) gained material being carried out halogenation treatment, in halogenation to final catalyst, zinc oxide weight content is 0.5%-20%, and zinc halide weight content is 10%-50%；(3) step (2) gained material is carried out silanization treatment, prepare halide preparing isobutene catalyst.This catalyst can optionally produce isobutene. by height.

Description

A kind of preparing isobutene catalyst and preparation method thereof

Technical field

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

Background technology

Isobutene. is a kind of important basic organic chemical industry raw material, and its derived product is numerous, and vertical industry chain is complicated, and consumption structure is diversified trend.Multiple high value-added product can be prepared for raw material, such as: multiple Organic Chemicals and the fine chemistry products such as butyl rubber, polyisobutylene, methyl tertiary butyl ether(MTBE), isoprene and lucite with isobutene..Owing to the market scale of isobutene. downstream product constantly expands, its imbalance between supply and demand will gradually highlight, and particularly under the background of petroleum resources exhaustion day by day, the yield of isobutene. has become the critical bottleneck of restriction downstream industry development.Therefore, the isobutene. syntheti c route of exploitation Non oil-based route, extremely the most urgent.

Methane is the main component of natural gas, the important research content during therefore methane trans-utilization just becomes gas chemical industry's technology.The most in recent years, develop fast development at shale gas, if it is possible to produce isobutene. from methane, an important approach will be provided for obtaining isobutene..But methane stable in properties, the most easily-activated, become the bottleneck of methane chemical utilization.Both at home and abroad many researcheres carry out methane activation, Study on Transformation one after another, among these, methane transformation technology again after halogen functional groupization, it is expected to become an important breakthrough mouth of a solution methane transformation technology difficult problem.

Bromomethane is important methane halides, can the many chemical products of preparation from bromomethane.Chinese patent CN 101041609A, CN 101284232A disclose one by methane at oxygen and HBr/H₂Being converted into bromomethane under the effect of O, then bromomethane reacts the method generating C3 ~ C13 mixing high-carbon hydrocarbon further, and the hydrocarbon selective of more than C5 is 70%.Wherein, HBr for methane bromination, then discharges in first reactor in second reactor, recovered after be used further in back reaction, it is achieved the recycling of HBr.(CN 102527427A, the Jieli such as Wang Ye He, Ting Xu, Zhihui Wang, et.al. Angew. Chem. Int. Ed. 2012,51,2438-2442) modified molecular sieve catalyst disclosing a kind of halide propylene and preparation method thereof.By using fluorochemical moditied processing molecular sieve, obtaining a kind of containing appropriate microporous structure and the catalyst of acidity, this catalyst can effectively be catalyzed halide and be converted into the reaction of propylene.Prepared catalyst one way bromomethane conversion ratio in the reaction that bromomethane is preparing propylene transformed is 35 ~ 99%, and the selectivity of propylene is 27 ~ 70%；In the reaction that chloromethanes is preparing propylene transformed, one way methyl chloride conversion rate is 30 ~ 99%, and the selectivity of propylene is 15 ~ 70%.Ivan M. Lorkovic et al. (Ivan M. Lorkovic, Aysen Yilmaz, Gurkan A. Yilmaz, et al. Catalysis Today, 2004,98,317-322) it is also proposed that generate bromo-hydrocarbons with bromine with the alkane reaction in natural gas, then on metal oxide catalyst, bromo-hydrocarbons is converted into dimethyl ether, methanol and metal bromide, obtain metal-oxide after metal bromide oxygen recovery and discharge simple substance bromine, completing the circulation of bromine.

At present, it is mainly methanol and dimethyl ether about purpose product in the existing document that halide converts, additionally also have acetic acid, higher hydrocarbons, ethylene and propylene, and in the technology with alkene as target product, product mostly is ethylene, propylene, and single selectivity of product is the highest, and not yet find the relevant report of bromomethane high selectivity isobutene..

Summary of the invention

For the deficiencies in the prior art, the invention provides a kind of halide preparing isobutene catalyst and preparation method thereof.

A kind of preparation method of preparing isobutene catalyst, including following process:

(1) zinc supported element and auxiliary agent zr element presoma on the alumina support, prepares catalyst precarsor after drying, roasting；

(2) step (1) gained material being carried out halogenation treatment, in halogenation to final catalyst, zinc oxide weight content is 0.5%-20%；Zinc halide weight content is 10%-50%；

(3) step (2) gained material is carried out silanization treatment, prepare halide preparing isobutene catalyst.

The inventive method, zinc element presoma described in step (1), auxiliary agent zirconium precursor body are inorganic salt or organic salt, preferably nitrate, chlorate, acetate, more preferably nitrate.

The inventive method, 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-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 inventive method, in step (3), silanization treatment process is that gas-phase silylation processes, processing the mixed gas that atmosphere is silylating reagent and hydrogen, concrete grammar is as follows: in continuous fixed bed reactor, the material after reduction is cooled to 130 DEG C-250 DEG C, preferably 160 DEG C-200 DEG C；Then by after preheated for silylating reagent, mixing with hydrogen and be passed through in reactor, in mixed atmosphere, silylating reagent volumn concentration is 1%-95%, preferably 5%-50%, more preferably 5%-10%, and surplus is hydrogen；The process time is 0.5h-10h, preferably 1h-8h, more preferably 1h-4h.

The inventive method, in step (3), described silylating reagent is one or more in alkylsiloxane, alkyl nitrogen silane, alkylchlorosilane, preferably MTES, hexamethyldisilazane, dichlorodimethylsilane, trim,ethylchlorosilane.Described silylating reagent is with SiO₂Meter weight percentage in the catalyst is 0.05%-10%.

A kind of halide preparing isobutene catalyst, it is characterised in that: in terms of weight content, zinc oxide content is 0.5%-20%, preferably 1%-15%, further preferred 1%-9%；Zinc halide content is 10%-50%, preferably 15%-45%, further preferred 18%-39%；Auxiliary agent oxide content is 0.1%-20%, preferably 0.1%-15%, more preferably 0.5%-10%.

In above-mentioned halide preparing isobutene catalyst, less than 450 DEG C total acid content (NH₃-TPD) it is 0.5mmol/g-1.3mmol/g, preferably 0.6mmol/g-1.2mmol/g, more preferably 0.7mmol-1.1mmol/g；The acid content of 250 DEG C-350 DEG C accounts for the 20%-90% of less than 450 DEG C total acid contents, preferably 30%-80%, more preferably 40%-80%.

The 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.Along with the carrying out of reaction, catalyst can be caused a certain degree of corrosion by hydrogen bromide, destroys the active center of catalyst, causes catalyst activity and selective isobutene to reduce.In the catalyst preparation process of the present invention, process the catalyst after activation, the on a catalyst outside protective layer forming a silane group in active center by the method for gas-phase silylation.By the protection of silane group, the highly acid atmosphere such as the hydrogen bromide destruction to active center can be avoided, such that it is able to improve catalyst stability in acid atmosphere.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 zinc nitrate, zirconium nitrate is dissolved in deionized water.Using equi-volume impregnating to be carried on alumina support, 120 DEG C of dry 6h, 350 DEG C of roasting 8h can prepare catalyst precarsor ZnO-ZrO₂/Al₂O₃.Using continuous fixed bed reactor, catalyst precarsor carries out under mixed atmosphere halogenation treatment, wherein 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.After halogenation treatment terminates, reactor is cooled to 160 DEG C, after hexamethyldisiloxane is preheated, mixes with hydrogen to be passed through in reactor catalyst is carried out gas-phase silylation process, wherein silylating reagent volume content in mixed atmosphere is 5%, and the process time is 1.5h.Preparing the catalyst after silanization treatment, its weight consists of ZnBr₂Content is 30%, and ZnO content is 4%, ZrO₂Content is 5%, and silylating reagent is with SiO₂Meter weight percentage in the catalyst is 0.66%.In catalyst, less than 450 DEG C total acid contents are 0.84mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 51.32% of less than 450 DEG C total acid contents.

Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and 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 93.71%, selective isobutene 80.05%.

Embodiment 2

Catalyst is prepared with embodiment 1, and difference is, silylating reagent is trim,ethylchlorosilane.Preparing the catalyst after silanization treatment, its weight consists of ZnBr₂Content is 30%, and ZnO content is 4%, ZrO₂Content is 5%, and silylating reagent is with SiO₂Meter weight percentage in the catalyst is 0.78%.In catalyst, less than 450 DEG C total acid contents are 0.80mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 49.19% 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 84.34%, selective isobutene 69.11%.

Embodiment 3

Catalyst is prepared with embodiment 1, and difference is, silylating reagent is MTES.Preparing the catalyst after silanization treatment, its weight consists of ZnBr₂Content is 30%, and ZnO content is 4%, ZrO₂Content is 5%, and silylating reagent is with SiO₂Meter weight percentage in the catalyst is 0.45%.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 48.72% 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 75.84%, selective isobutene 72.63%.

Embodiment 4

Catalyst is prepared with embodiment 1, and difference is, silanization treatment temperature is 180 DEG C.Preparing the catalyst after silanization treatment, its weight consists of ZnBr₂Content is 30%, and ZnO content is 4%, ZrO₂Content is 5%, and silylating reagent is with SiO₂Meter weight percentage in the catalyst is 0.87%.In catalyst, less than 450 DEG C total acid contents are 0.77mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 47.1% 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 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 92.77%, selective isobutene 75.10%.

Embodiment 5

Catalyst is prepared with embodiment 1, and difference is, silanization treatment temperature is 200 DEG C.Preparing the catalyst after silanization treatment, its weight consists of ZnBr₂Content is 30%, and ZnO content is 4%, ZrO₂Content is 5%, and silylating reagent is with SiO₂Meter weight percentage in the catalyst is 1.05%.In catalyst, less than 450 DEG C total acid contents are 0.83mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 51.82% 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 80.81%, selective isobutene 58.15%.

Embodiment 6

Catalyst is prepared with embodiment 1, and difference is, silylating reagent volume content in mixed atmosphere is 50%.Preparing the catalyst after silanization treatment, its weight consists of ZnBr₂Content is 30%, and ZnO content is 4%, ZrO₂Content is 5%, and silylating reagent is with SiO₂Meter weight percentage in the catalyst is 2.84%.In catalyst, less than 450 DEG C total acid contents are 0.79mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 48.4% 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 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 66.78%, selective isobutene 40.85%.

Embodiment 7

Catalyst is prepared with embodiment 1, and difference is, silylating reagent volume content in mixed atmosphere is 95%.Preparing the catalyst after silanization treatment, its weight consists of ZnBr₂Content is 30%, and ZnO content is 4%, ZrO₂Content is 5%, and silylating reagent is with SiO₂Meter weight percentage in the catalyst is 4.51%.In catalyst, less than 450 DEG C total acid contents are 0.8mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 48.72% 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 61.59%, selective isobutene 36.03%.

Embodiment 8

Catalyst is prepared with embodiment 1, and difference is, the silanization treatment time is 4h.Preparing the catalyst after silanization treatment, its weight consists of ZnBr₂Content is 30%, and ZnO content is 4%, ZrO₂Content is 5%, and silylating reagent is with SiO₂Meter weight percentage in the catalyst is 1.26%.In catalyst, less than 450 DEG C total acid contents are 0.75mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 46.12% 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 91.75%, selective isobutene 79.34%.

Comparative example 1

Catalyst is prepared with embodiment 1.Reaction condition is with embodiment 1, and difference is, does not carries out activation processing during reaction.Bromomethane conversion ratio 1.59%, selective isobutene 0%.

Comparative example 2

Catalyst is prepared with embodiment 1, and difference is, does not carries out halogenation treatment.Reaction condition is with embodiment 1, bromomethane conversion ratio 89.81%, selective isobutene 0%.

Comparative example 3

With embodiment 1, difference is to activate as zinc zinc bromide completely.Bromomethane conversion ratio 0.85%, selective isobutene 0%.

Claims (22)

1. the preparation method of a preparing isobutene catalyst, it is characterised in that: include following process:

(1) zinc supported element and auxiliary agent zr element presoma on the alumina support, prepares catalyst precarsor after drying, roasting；

(2) step (1) gained material being carried out halogenation treatment, in halogenation to final catalyst, zinc oxide weight content is 0.5%-20%, and zinc halide weight content is 10%-50%；

(3) step (2) gained material is carried out silanization treatment, prepare halide preparing isobutene catalyst.

Method the most according to claim 1, it is characterised in that: zinc element presoma described in step (1), auxiliary agent zirconium precursor body are nitrate, chlorate or acetate.

Method the most according to claim 1, it is characterised in that: in step (1), baking temperature is 50 DEG C-200 DEG C；Drying time is 1h-48h；Sintering temperature is 200 DEG C-800 DEG C；Roasting time is 1h-24h.

Method the most according to claim 3, it is characterised in that: in step (1), baking temperature is 60 DEG C-150 DEG C；Drying time is 2h-36h；Sintering temperature is 300 DEG C-600 DEG C；Roasting time is 2h-16h.

Method the most according to claim 1, it is characterised in that: in step (2), halogenation treatment process is as follows: is placed in continuous fixed bed reactor by step (1) material, is warming up to 150 DEG C-400 DEG C under inert atmosphere；Then passing to halide and noble gas gaseous mixture, in gaseous mixture, halide volumn concentration is 1%-95%；The process time is 0.5h-16h；Processing pressure is 0.1MPa-0.5MPa；Volume space velocity is 50h^-1-1000 h^-1。

Method the most according to claim 5, it is characterised in that: it is warming up to 180 DEG C-350 DEG C under inert atmosphere；In gaseous mixture, halide volumn concentration is 10%-90%；The process time is 1h-8h；Processing pressure is 0.1MPa-0.3MPa；Volume space velocity is 100 h^-1-500 h^-1。

Method the most according to claim 1, it is characterised in that: in step (3), silanization treatment process is that gas-phase silylation processes, and processes the mixed gas that atmosphere is silylating reagent and hydrogen.

Method the most according to claim 7, it is characterised in that: in continuous fixed bed reactor, the material after reduction is cooled to 130 DEG C-250 DEG C；Then by after preheated for silylating reagent, mixing with hydrogen and be passed through in reactor, in mixed atmosphere, silylating reagent volumn concentration is 1%-95%；The process time is 0.5h-10h.

Method the most according to claim 8, it is characterised in that: in continuous fixed bed reactor, the material after reduction is cooled to 160 DEG C-200 DEG C；Then by after preheated for silylating reagent, mixing with hydrogen and be passed through in reactor, in mixed atmosphere, silylating reagent volumn concentration is 5%-50%；The process time is 1h-8h.

Method the most according to claim 1, it is characterised in that: in step (3), silylating reagent is alkylsiloxane, alkyl nitrogen silane or alkylchlorosilane.

11. methods according to claim 11, it is characterised in that: silylating reagent is one or more in MTES, hexamethyldisilazane, dichlorodimethylsilane, trim,ethylchlorosilane.

12. methods according to claim 1, it is characterised in that: in step (3), silylating reagent is with SiO₂Meter weight percentage in the catalyst is 0.05%-10%.

Catalyst prepared by 13. claim 1 to 12 either method, it is characterised in that: in terms of weight content, zinc oxide content is 0.5%-20%；Zinc halide content is 10%-50%；Auxiliary agent zirconia content is 0.1%-20%.

14. catalyst according to claim 13, it is characterised in that: in terms of weight content, zinc oxide content is 1%-15%；Zinc halide content is 15%-45%；Auxiliary agent zirconia content is 0.1%-15%.

15. catalyst according to claim 14, it is characterised in that: in terms of weight content, zinc oxide content is 1%-9%；Zinc halide content is 18%-39%；Auxiliary agent zirconia content is 0.5%-10%.

16. catalyst according to claim 14, it is characterised in that: in catalyst, less than 450 DEG C total acid contents are 0.5mmol/g-1.3mmol/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.

Catalyst application in halide preparing isobutene described in 17. claim 14, 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.

18. application according to claim 17, 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, needing before charging catalyst is carried out reduction treatment, the content of halogen being reduced in catalyst is the 30%-80% of total halogen content in reduction procatalyst.

19. application according to claim 17, 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, after 0.1MPa-0.5MPa processes 2h-16h, be down to reaction temperature and be passed through halide and react, in described gaseous mixture, hydrogen volume percentage composition is 10%-95%.

20. application stated according to claim 19, it is characterised in that: by catalyzer temperature-elevating to 350 DEG C-550 DEG C under inert atmosphere；Then passing to air speed is 500h^-1-1000h^-1Hydrogen or the mixed gas of hydrogen and noble gas, after 0.1MPa-0.3MPa processes 4h-8h, be down to reaction temperature and be passed through halide and react, in described gaseous mixture, hydrogen volume percentage composition is 30%-90%.

21. application according to claim 17, 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%.

22. application according to claim 17, it is characterised in that: halide raw material is a halide, methylene halide or three halides.