CN106140216A

CN106140216A - A kind of P Modification halide preparing isobutene catalyst and preparation method thereof

Info

Publication number: CN106140216A
Application number: CN201510135816.XA
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: CN106140216B

Abstract

Open a kind of P Modification halide preparing isobutene catalyst of the present invention and preparation method thereof.Described catalyst content meter by weight, zinc oxide content is 0.5%-20%；Zinc halide content is 10%-50%；Phosphorus counts weight content in the catalyst as 0.1%-20% with element.Catalyst preparation includes following process: (1) uses step impregnation method to be first carried on alumina support by P elements presoma, prepares P Modification aluminium oxide after drying, roasting；Then proceed to zinc supported elemental precursor, catalyst precarsor after drying, roasting, can be prepared；(2) step (1) gained catalyst precarsor is carried out halogenation treatment and can prepare halide preparing isobutene catalyst.This catalyst can prepare high selective isobutene..

Description

A kind of P Modification halide preparing isobutene catalyst and preparation method thereof

Technical field

The present invention relates to a kind of P Modification halide preparing isobutene catalyst and preparation method thereof.

Background technology

Isobutene. is a kind of important basic organic chemical industry raw material, and 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, isobutene. yield has become the critical bottleneck of restriction downstream industry development.Therefore, the isobutene. syntheti c route of exploitation non-petroleum base, 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

It is an advantage of the invention to provide the catalyst of a kind of P Modification halide preparing isobutene.It is a further object of the invention to provide the preparation method of above-mentioned catalyst.

A kind of halide preparing isobutene catalyst, it is characterised in that: based on the weight content of catalyst, 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%；Vector contg 40%-90%, preferably 50%-85%, further preferred 55%-80%；Described zinc halide includes one or more in zinc fluoride, zinc chloride, zinc bromide, zinc iodide, preferably zinc bromide；Described carrier is aluminium oxide.

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%.

Described auxiliary agent phosphorus is in terms of element, and mass percent in the catalyst is 0.1%-20%, preferably 0.1%-15%, more preferably 0.5%-10%.

The preparation method of the above-mentioned catalyst of the present invention, comprises the steps:

(1) use infusion process to be first carried on alumina support by P elements presoma, after drying, roasting, prepare P Modification aluminium oxide；Then proceed to zinc supported elemental precursor, catalyst precarsor after drying, roasting, can be prepared；

(2) step (1) gained catalyst precarsor is carried out halogenation treatment；Halide preparing isobutene catalyst can be prepared.

The inventive method, described in step (1), zinc element presoma is inorganic salt or organic salt, preferably zinc nitrate, zinc chloride, zinc acetate, more preferably zinc nitrate.

The inventive method, described in step (1), the presoma of P elements is one or more in the forms such as oxide, halogenide, oxyhalide, phosphoric acid, phosphate, preferably phosphoric acid.

The catalyst carrier that the present invention relates to can be prepared by the method for it is well known that.The present invention relates to catalyst and can make suitable particle shape according to the needs used, as made bar shaped, sheet shape, cylindricality, spherical etc..Shaping can be carried out by this area general knowledge.

The inventive method, 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-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.

The inventive method, described in step (1), 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.

The inventive method, halogenation treatment described in step (2), refer to use gas phase halogen contained compound that the sample of load zinc oxide is processed.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 zinc oxide, 150 DEG C-400 DEG C it are warming up under inert atmosphere, preferably 180 DEG C-350 DEG C, more preferably 200 DEG C-300 DEG C, being passed through gas phase halogen contained compound gas, gas space velocity is 50h^-1-1000 h^-1, preferably 100h^-1-500h^-1；Can carry out at normal pressure during process, it is also possible to carry out under a certain pressure, system pressure is 0.1MPa-0.5MPa, preferably 0.1MPa-0.3MPa, and 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, preferably 0.1MPa-3MPa；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, at 0.1MPa-0.5MPa, preferably 0.1MPa-0.3MPa, after processing 2h-16h, preferably 4h-8h, be down to reaction temperature and be passed through halide and react.In described gaseous mixture, hydrogen volume percentage composition is 10%-95%, preferably 30%-90%, more preferably 50%-90%.

In above-mentioned application, raw material can also be the mixed gas of halide and noble gas, and in mixed gas, the volumetric concentration of halide is 10%-90%, preferably 30%-80%.

Noble gas involved in above-mentioned application is the gas that nitrogen, argon, helium etc. do not occur chemical reaction under the conditions of involved in the present invention, preferably nitrogen.

In above-mentioned application, halide raw material can be a halide, methylene halide, three halides, preferably one bromomethane, methylene bromide, bromoform, more preferably one bromomethane.

In above-mentioned application, the reaction of halide preparing isobutene can be carried out, such as fixed bed, fluid bed, fixed fluidized bed, moving bed, the reactor of the form such as slurry bed system or ebullated bed, preferably fixed bed, fluidized-bed reactor in existing any form reactor.

Compared with prior art, bromomethane height can be optionally converted into isobutene. by the method that the present invention relates to.Use P Modification can improve the acidic site of catalyst surface by the inventive method, for the acid site that the conversion offer of bromomethane is suitable.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 phosphoric acid to be dissolved in deionized water, use equi-volume impregnating to be carried on alumina support, 120 DEG C of dry 4h, 350 DEG C of roasting 8h, prepare P Modification alumina support.Then weigh appropriate zinc nitrate to be dissolved in deionized water, use equi-volume impregnating to be carried on P Modification alumina support, 80 DEG C of dry 8h, 600 DEG C of roasting 4h, prepare catalyst precarsor ZnO-P/Al₂O₃.Being placed in continuous fixed bed reactor by 5g catalyst precarsor, use a bromomethane to process catalyst precarsor, treatment conditions are: 230 DEG C, 0.1MPa, 100h^-1, the time is 4h.Prepare halide preparing isobutene catalyst, be designated as C-01.Catalyst weight consists of ZnBr₂Weight content is 31.3%, and ZnO weight content is 3.7%, and P weight content is 3%.In catalyst C-01, 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 62.33% 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.Reaction result is shown in Table 1.

Embodiment 2

With embodiment 1, prepared catalyst is designated as C-02, and difference is, catalyst weight consists of ZnBr₂Weight content is 10.4%, and ZnO weight content is 1.2%, and P weight content is 3%.In catalyst C-02, less than 450 DEG C total acid contents are 0.68mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 49.86% 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.Reaction result is shown in Table 1.

Embodiment 3

With embodiment 1, prepared catalyst is designated as C-03, and difference is, catalyst weight consists of ZnBr₂Weight content is 43.3%, and ZnO weight content is 7.8%, and P weight content is 3%.In catalyst C-03, less than 450 DEG C total acid contents are 0.89mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 66.56% 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.Reaction result is shown in Table 1.

Embodiment 4

With embodiment 1, prepared catalyst is designated as C-04, and difference is, catalyst weight consists of ZnBr₂Weight content is 30.6%, and ZnO weight content is 3.8%, and P weight content is 1%.Reaction condition is with embodiment 1.In catalyst C-04, less than 450 DEG C total acid contents are 0.61mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 45.62% 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.Reaction result is shown in Table 1.

Embodiment 5

With embodiment 1, prepared catalyst is designated as C-05, and difference is, catalyst weight consists of ZnBr₂Weight content is 31.5%, and ZnO weight content is 3.6%, and P weight content is 6%.Reaction condition is with embodiment 1.In catalyst C-05, less than 450 DEG C total acid contents are 0.73mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 54.59% of less than 450 DEG C total acid contents.

Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane, and 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.Reaction result is shown in Table 1.

Embodiment 6

With embodiment 1, prepared catalyst is designated as C-06, and difference is, catalyst weight consists of ZnBr₂Weight content is 29.6%, and ZnO weight content is 4.0%, and P weight content is 10%.Reaction condition is with embodiment 1.In catalyst C-06, less than 450 DEG C total acid contents are 1.02mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 76.28% 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.Reaction result is shown in Table 1.

Embodiment 7

With embodiment 1, difference is that the halogenation time is 2h, and catalyst is designated as C-07.Catalyst weight consists of ZnBr₂Weight content is 23.5%, and ZnO weight content is 6.5%, and P weight content is 3%.Reaction condition is with embodiment 1.In catalyst C-07, less than 450 DEG C total acid contents are 0.81mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 60.58% of less than 450 DEG C total acid contents.

Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 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.Reaction result is shown in Table 1.

Embodiment 8

With embodiment 1, difference is that the halogenation time is 6h, and catalyst is designated as C-08.Catalyst weight consists of ZnBr₂Weight content is 33.9%, and ZnO weight content is 2.8%, and P weight content is 3%.Reaction condition is with embodiment 1.In catalyst C-08, less than 450 DEG C total acid contents are 0.90mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 62.04% 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.Reaction result is shown in Table 1.

Embodiment 9

With embodiment 1, difference is that halogenation temperature is 250 DEG C, and catalyst is designated as C-09.Catalyst weight consists of ZnBr₂Weight content is 26.1%, and ZnO weight content is 5.6%, and P weight content is 3%.Reaction condition is with embodiment 1.In catalyst C-09, less than 450 DEG C total acid contents are 0.93mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 64.11% of less than 450 DEG C total acid contents.Reaction result is shown in Table 1.

Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 200h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h^-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 61.62%.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.

Embodiment 10

With embodiment 1, difference is that halogenation temperature is 300 DEG C, and catalyst is designated as C-10.Catalyst weight consists of ZnBr₂Weight content is 34.9%, and ZnO weight content is 2.4%, and P weight content is 3%.Reaction condition is with embodiment 1.In catalyst C-10, less than 450 DEG C total acid contents are 1.05mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 72.38% of less than 450 DEG C total acid contents.

Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 200h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h^-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 60.64%.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.

Comparative example 1

With embodiment 1, difference is that catalyst is unactivated during preparing isobutene.Reaction result is shown in Table 1.

Comparative example 2

With embodiment 1, difference is in catalyst preparation process not carry out halogenation treatment.Reaction result is shown in Table 1.

Comparative example 3

With embodiment 1, even if difference activates zinc bromide Restore All completely during being preparing isobutene be zinc.Reaction result is shown in Table 1.

Table 1

Claims

1. a P Modification halide preparing isobutene catalyst, it is characterized in that: based on the weight content of catalyst, zinc oxide content is 0.5%-20%, zinc halide content is 10%-50%, phosphorus content is 0.1%-20%, vector contg is 40%-90%, and described zinc halide includes that one or more in zinc fluoride, zinc chloride, zinc bromide, zinc iodide, described carrier are aluminium oxide.

Catalyst the most according to claim 1, it is characterised in that: zinc oxide content is 1%-15%, and zinc halide content is 15%-45%, and phosphorus content is 0.1%-15%, and vector contg is 50%-85%, and described zinc halide is zinc bromide.

Catalyst the most according to claim 1, it is characterised in that: zinc oxide content is 1%-9%, and zinc halide content is 18%-39%, and phosphorus content is 0.5%-10%, and vector contg is 55%-80%.

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 the described catalyst of one of claim 1-6, it is characterised in that: include following process: (1) uses infusion process to be first carried on alumina support by P elements presoma, after drying, roasting, prepare P Modification aluminium oxide；Then proceed to zinc supported elemental precursor, catalyst precarsor after drying, roasting, can be prepared；(2) step (1) gained catalyst precarsor is carried out halogenation treatment and can prepare halide preparing isobutene catalyst.

Method the most according to claim 7, it is characterised in that: described in step (1), zinc element presoma is one or more in zinc nitrate, zinc chloride, zinc acetate.

Method the most according to claim 7, it is characterised in that: described in step (1), the presoma of P elements is phosphoric acid.

Method the most according to claim 7, it is characterised in that: in step (1), alumina support is shaped as bar shaped, sheet shape, cylindricality or spherical.

11. methods according to claim 7, it is characterised in that: described in step (1), baking temperature is 50 DEG C-200 DEG C；Drying time is 1h-24h.

12. methods according to claim 7, it is characterised in that: described in step (1), sintering temperature is 200 DEG C-800 DEG C；Roasting time is 1h-24h.

13. methods according to claim 7, it is characterised in that: halogenation treatment described in step (2) uses gas phase halogen contained compound to process step (1) gained sample.

14. methods according to claim 13, it is characterised in that: halogen contained compound is one or more in a halide, methylene halide, three halides.

15. methods according to claim 13, 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%.

16. methods according to claim 13, 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.

17. methods according to claim 16, 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 in preparing isobutene of one of 18. claim 1 to 6 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 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.

19. application according to claim 18, 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.

20. application according to claim 18, 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%.

21. application according to claim 20, 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%.

22. application according to claim 18, 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%.

23. application according to claim 22, it is characterised in that: noble gas is one or more in nitrogen, argon, helium.

24. application according to claim 18, it is characterised in that: halide raw material is one or more in a halide, methylene halide, three halides.

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

26. application according to claim 18, 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.