CN106140213B - A kind of halide preparing isobutene catalyst of additive modification and its preparation method and application - Google Patents

Abstract

The present invention discloses a kind of halide preparing isobutene catalyst of additive modification and its preparation method and application.Zinc oxide weight content is 0.5%-20% in the catalyst；Zinc halide weight content is 10%-50%；Zirconium oxide weight content is 0.1%-20%；Neodymia weight content is 0.1%-20%；Surplus is alumina catalyst support.Catalyst preparation process is as follows：（1）Catalyst precarsor is made using sol-gal process；（2）To step（1）The catalyst precarsor of gained carries out halogenation treatment, and halide preparing isobutene catalyst is made.The catalyst can significantly improve the selectivity of isobutene.

Description

A kind of halide preparing isobutene catalyst of additive modification and preparation method thereof and Using

Technical field

The present invention relates to a kind of catalyst and its preparation method and application, relate in particular to a kind of halide high selection The catalyst and its preparation method and application of property preparing isobutene, the halide isobutyl of more particular to a kind of additive modification Alkene catalyst and its preparation method and application.

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, disappears It is in diversified trend to take structure.A variety of high value-added products can be prepared by raw material of isobutene, such as：It is butyl rubber, poly- different A variety of Organic Chemicals such as butylene, methyl tertiary butyl ether(MTBE), isoprene and organic glass and fine chemistry product.Due to isobutyl The market scale of alkene downstream product constantly expands, and imbalance between supply and demand will be protruded gradually, especially in petroleum resources increasingly depleted Under background, the yield of isobutene has become the critical bottleneck for restricting downstream industry development.Therefore, the isobutyl of Non oil-based route is developed Alkene preparation route is extremely urgent.

Methane is the main component of natural gas, therefore methane trans-utilization important grinding of just becoming in gas chemical industry's technology Study carefully content.Especially in recent years, it develops and uses and grows rapidly in shale gas, if it is possible to produce isobutene from methane, just An important approach can be provided to obtain isobutene.But methane property is stablized, and it is not easily-activated, become methane chemical utilization Bottleneck.Domestic and international many researchers carry out methane activation, Study on Transformation one after another, among these, methane after halogen functional groupization again Transformation technology is expected to become an important breakthrough mouth for solving methane transformation technology problem.

Bromomethane is important methane halides, and one many chemical products can be prepared from bromomethane.Chinese patent CN 101041609A, CN 101284232A disclose it is a kind of by methane in oxygen and HBr/H₂Bromo first is converted under the action of O Alkane, then bromomethane further react the method for generating C3 ~ C13 mixing high-carbon hydrocarbons, the hydrocarbon selective of C5 or more is 70%. Wherein, HBr is used for methane bromination in first reactor, then discharges in second reactor, is used further to after recovered In back reaction, the recycling of HBr is realized.Wang Ye etc.（CN 102527427A, Jieli He, Ting Xu, Zhihui Wang, et.al. Angew. Chem. Int. Ed. 2012, 51, 2438-2442）Disclose a kind of halide system third Modified molecular sieve catalyst of alkene and preparation method thereof.By using fluorochemical moditied processing molecular sieve, obtains one kind and contain There are the catalyst of appropriate microporous structure and acidity, the catalyst that can effectively be catalyzed the reaction that halide is converted into propylene. Prepared catalyst one way bromomethane conversion ratio in the preparing propylene transformed reaction of bromomethane is 35 ~ 99%, the selectivity of propylene It is 27 ~ 70%；One way methyl chloride conversion rate is 30 ~ 99% in the preparing propylene transformed reaction of chloromethanes, 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 generating bromo with the alkane reaction in bromine and natural gas Hydrocarbon, then converts bromo-hydrocarbons to dimethyl ether, methanol and metal bromide on metal oxide catalyst, and metal bromide is used Metal oxide is obtained after oxygen recovery and releases simple substance bromine, completes the cycle of bromine.

Currently, being mainly methanol and dimethyl ether about purpose product in the existing literature of halide conversion, in addition also have Acetic acid, higher hydrocarbons, ethylene and propylene, and using alkene as in the technology of target product, product is mostly ethylene, propylene, and single One selectivity of product is not high, and not yet finds the relevant report of bromomethane high selectivity isobutene.

Invention content

In view of the deficiencies of the prior art, the present invention provide a kind of additive modification halide preparing isobutene catalyst and its Preparation method and application

A kind of halide preparing isobutene catalyst of additive modification, zinc oxide weight content is in the catalyst 0.5%-20%, preferably 1%-15%, further preferred 1%-9%；Zinc halide weight content is 10%-50%, preferably 15%-45%, into one Walk preferred 18%-39%；Zirconium oxide weight content is 0.1%-20%, preferably 0.1%-15%, further preferably 0.5%-10%；Oxygen Change neodymium weight content is 0.1%-20%, preferably 0.1%-15%, further preferably 0.5%-10%；Surplus is alumina catalyst support.

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

The preparation method of above-mentioned catalyst, includes the following steps：

（1）Zinc salt, zirconates, neodymium salt and aluminium salt are dissolved in the water and are configured to the solution that pH value is 2 ~ 3；At 60 DEG C ~ 90 DEG C Lower addition complexing agent, return stirring 6h ~ 10h so that moisture is constantly evaporated up to form thick gel in solution, then carries out Aging；Gel after aging is become into dry glue shape by dry, catalyst precarsor can be made after fired；

（2）To step（1）The catalyst precarsor of gained carries out halogenation treatment, and halide preparing isobutene catalyst is made.

The method of the present invention step（1）In, the zinc salt, zirconates, neodymium salt and aluminium salt are its nitrate, sulfate or halogenation Salt etc., preferably nitrate；The complexing agent is citric acid, one kind in ethylene glycol or two kinds of mixing, preferably citric acid.

The method of the present invention, step（1）Described in ageing process can be aged at room temperature, or in certain constant temperature item Aging under part, aging temperature be 10 DEG C -90 DEG C, preferably 50 DEG C -80 DEG C, ageing time 1h-72h, preferably 12h-48h.

The method of the present invention, step（1）In further include dry and roasting process.Drying temperature is 50 DEG C -200 DEG C, preferably 60 DEG C -150 DEG C, more preferably 100 DEG C -120 DEG C；Drying time is 1h-48h, preferably 2h-36h, more preferably 2h-24h； Can be vacuum drying when dry, or it is dry under the conditions of inert gas shielding, it can also dry in air atmosphere；Roasting It is 200 DEG C -800 DEG C to burn temperature, preferably 300 DEG C -600 DEG C, more preferably 350 DEG C -500 DEG C；Roasting time is 1h-24h, excellent It is selected as 2h-16h, more preferably 4h-8h；Can be to be dry under the conditions of inert gas shielding when roasting, it can also be in air atmosphere Lower drying.

The present invention relates to catalyst to need to be made suitable particle shape according to what is used, be such as made bar shaped, piece shape, Cylindricality, spherical shape etc..Forming can be carried out by this field general knowledge.

The method of the present invention, step（2）Middle halogenation treatment process is as follows：By step（1）It is solid that resulting material is placed in continuous flowing In fixed bed reactor, 150 DEG C -400 DEG C, preferably 180 DEG C -350 DEG C, more preferably 200 DEG C -300 are warming up under inert atmosphere ℃；Halide and inert gas gaseous mixture are then passed to, halide volumn concentration is 1%-95% in gaseous mixture, preferably For 10%-90%, surplus is inert gas；Processing time is 0.5h-16h, preferably 1h-8h, more preferably 1h-4h；Processing pressure Power 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, using 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, need to carry out reduction treatment, reduction to catalyst before charging It is 20%-90%, the preferably 30%-80% for restoring total halogen content in procatalyst to the content of halogen in catalyst, it is further excellent Select 40%-80%.

In above application, a kind of specific reduction treatment process is as follows：Under inert atmosphere by catalyzer temperature-elevating to 300 DEG C- 600 DEG C, preferably 350 DEG C -550 DEG C；It is 200h to then pass to air speed^-1-2000h^-1, preferably 500h^-1-1000h^-1Hydrogen Or the mixed gas of hydrogen and inert gas, 2h-16h is handled in 0.1MPa-0.5MPa, preferably 0.1MPa-0.3MPa, preferably After 4h-8h, it is down to reaction temperature and is passed through halide and reacted.Hydrogen volume percentage composition is 10%- in the gaseous mixture 95%, preferably 30%-90%, more preferably 50%-90%.

In above application, raw material may be the mixed gas of halide and inert gas, halogenated first in mixed gas The volumetric concentration of alkane is 10%-90%, preferably 30%-80%.

Involved inert gas is that nitrogen, argon gas, helium etc. are not sent out under the conditions of involved in the present invention in above application The gas of biochemical reaction, preferably nitrogen.

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

In above application, the reaction of halide preparing isobutene can carry out in existing any form reactor, such as fixed Bed, fluid bed, fixed fluidized bed, moving bed, the reactor of the forms such as slurry bed system or ebullated bed, preferably fixed bed, fluid bed Reactor.

Compared with prior art, method of the present invention can by bromomethane it is highly selective be converted into isobutene.This Invention improves the dispersibility of each component in catalyst using the preparation method of collosol and gel, by the way that the presoma of each component is pre- It is first dissolved in solvent and forms homogeneous phase solution, by solution reaction step, can make auxiliary agent, active metal and carrier in catalyst Realize the uniform mixing on molecular level；Meanwhile the content of each component in catalyst can also be accurately controlled using this method.It is molten Each component has higher dispersion degree in catalyst prepared by sol-gel, to also improve the activity of catalyst, halogenated The reaction of methane conversion shows higher selective isobutene.The present invention relates to bromomethanes to convert preparing isobutene catalyst system Preparation Method is simple, is easy to industrialize.Bromomethane conversion preparing isobutene method of the present invention mild, selectivity of product with reaction condition The advantages that high, industrialization easy to implement, application prospect are boundless.

Specific implementation mode

The technology contents and effect further illustrated the present invention with reference to embodiment, but do not limit the present invention.Catalyst Acidimetric estimation uses NH₃- TPD methods, the instrument model used is 2920 chemistry of MICROMERITICS companies of U.S. AutoChem Adsorption instrument, specific continuous mode are as follows：Sample is cooled to 150 DEG C after 1 hour with helium purge at 450 DEG C, introduces ammonia and helium The mixed gas of gas, ammonia volume content 10%, Pulse adsorption reach balance five times；Helium purge 2 hours, then with 10 DEG C/min Heating rate temperature programming carry out ammonia be desorbed to 450 DEG C；Ammonia after desorption is detected using TCD detectors, quantitative to calculate catalysis Agent Surface acidity.

Embodiment 1

Zinc nitrate, zirconium nitrate, neodymium nitrate, aluminum nitrate are weighed in catalyst ratio to be added to the water, it is 2 to adjust solution ph； Citric acid, return stirring 6h are added at 70 DEG C so that moisture is constantly evaporated up to form thick gel in solution, and gel exists Aging 3 days at room temperature；The colloid is put into baking oven drying 24 hours at 80 DEG C, becomes dry glue shape；Then it is roasted at 400 DEG C 8 hours, catalyst precarsor ZnO-ZrO can be made₂-Nd₂O₃/Al₂O₃.Using continuous fixed bed reactor, in a bromomethane Catalyst precarsor is handled under atmosphere, monobromo methane volumetric content is 30% in monobromo methane blended gas, and surplus is nitrogen, processing Condition is 250 DEG C, 0.1MPa, 100h^-1, time 2h.Catalyst is made, weight group becomes ZnBr₂Content is 27.7%, ZnO It is 5%, Nd contents in terms of oxide is 5% that content, which is 1.2%, Zr contents in terms of oxide,.450 DEG C or less total acid contents in catalyst For 0.78mmol/g, 250 DEG C -350 DEG C of acid content accounts for the 60.82% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 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, reaction Pressure is 1MPa（Absolute pressure）, air speed 500h^-1, it is passed through unstripped gas procatalyst and activates in a hydrogen atmosphere, reducing condition 400 DEG C, 0.2MPa（Absolute pressure）, 1000h^-1, recovery time 4h, it is halogen in reduction procatalyst to restore the content of halogen in rear catalyst The 65.28% of plain total content.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 66.28%, selective isobutene 46.55%。

Embodiment 2

Zinc nitrate, zirconium nitrate, neodymium nitrate, aluminum nitrate are weighed in catalyst ratio to be added to the water, it is 3 to adjust solution ph； Citric acid, return stirring 8 hours are added at 80 DEG C so that moisture is constantly evaporated up to form thick gel in solution, coagulates Glue aging 3 days at room temperature；The colloid is put into baking oven drying 16 hours at 100 DEG C, becomes dry glue shape；Then at 450 DEG C Lower roasting 4 hours, can be made catalyst precarsor ZnO-ZrO₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, one Catalyst precarsor is handled under bromomethane atmosphere, monobromo methane volumetric content is 50% in monobromo methane blended gas, and surplus is nitrogen Gas, treatment conditions are 230 DEG C, 0.2MPa, 200h^-1, time 4h.Catalyst is made, weight group becomes ZnBr₂Content is 31.2%, ZnO content 3.7%, Zr contents in terms of oxide are that 5%, Nd contents in terms of oxide are 5%.In catalyst 450 DEG C with Lower total acid content is 0.85mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 51.23% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 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, reaction Pressure is 2MPa（Absolute pressure）, air speed 200h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa（Absolute pressure）, 800h^-1, recovery time 4h, after reduction Content of halogen in catalyst is restore total halogen content in procatalyst 51.7%.After stable reaction one hour, sampling point Analysis.Bromomethane conversion ratio 87.23%, selective isobutene 62.59%.

Embodiment 3

In catalyst ratio zinc nitrate, zirconium nitrate, neodymium nitrate, aluminum nitrate is weighed to be added to the water, adjust solution ph be 2 ~ 3；Citric acid, return stirring 10 hours are added at 90 DEG C so that moisture is constantly evaporated up to form thick gel in solution, Gel aging 3 days at room temperature；The colloid is put into baking oven drying 12 hours at 120 DEG C, becomes dry glue shape；Then 350 It is roasted 8 hours at DEG C, catalyst precarsor ZnO-ZrO can be made₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, Catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 70% in monobromo methane blended gas, and surplus is nitrogen Gas, treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, time 2h.Catalyst is made, weight group becomes ZnBr₂Content is 6.9%, ZnO content 1.9%, Zr contents in terms of oxide are that 5%, Nd contents in terms of oxide are 5%.In catalyst 450 DEG C with Lower total acid content is 0.71mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 65.31% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 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, reaction Pressure is 3MPa（Absolute pressure）, air speed 350h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing Hydrogen volume content is 50% in gas, and reducing condition is 500 DEG C, 0.1MPa（Absolute pressure）, 500h^-1, recovery time 4h, after reduction Content of halogen in catalyst is restore total halogen content in procatalyst 45.66%.After stable reaction one hour, sampling point Analysis.Bromomethane conversion ratio 54.95%, selective isobutene 61.57%.

Embodiment 4

In catalyst ratio zinc nitrate, zirconium nitrate, neodymium nitrate, aluminum nitrate is weighed to be added to the water, adjust solution ph be 2 ~ 3；Citric acid, return stirring 6 hours are added at 80 DEG C so that moisture is constantly evaporated up to form thick gel in solution, Gel aging 3 days at room temperature；The colloid is put into baking oven drying 12 hours at 120 DEG C, becomes dry glue shape；Then 350 It is roasted 8 hours at DEG C, catalyst precarsor ZnO-ZrO can be made₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, Catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 50% in monobromo methane blended gas, and surplus is nitrogen Gas, treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, time 2h.Catalyst is made, weight group becomes ZnBr₂Content is 10.4%, ZnO content 7.5%, Zr contents in terms of oxide are that 5%, Nd contents in terms of oxide are 5%.In catalyst 450 DEG C with Lower total acid content is 0.93mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 39.91% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 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, reaction Pressure is 2MPa（Absolute pressure）, air speed 350h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing Hydrogen volume content is 70% in gas, and reducing condition is 350 DEG C, 0.3MPa（Absolute pressure）, 800h^-1, recovery time 6h, after reduction Content of halogen in catalyst is restore total halogen content in procatalyst 55.9%.After stable reaction one hour, sampling point Analysis.Bromomethane conversion ratio 89.66%, selective isobutene 82.08%.

Embodiment 5

In catalyst ratio zinc nitrate, zirconium nitrate, neodymium nitrate, aluminum nitrate is weighed to be added to the water, adjust solution ph be 2 ~ 3；Citric acid, return stirring 6 hours are added at 80 DEG C so that moisture is constantly evaporated up to form thick gel in solution, Gel aging 3 days at room temperature；The colloid is put into baking oven drying 12 hours at 120 DEG C, becomes dry glue shape；Then 350 It is roasted 8 hours at DEG C, catalyst precarsor ZnO-ZrO can be made₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, Catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 50% in monobromo methane blended gas, and surplus is nitrogen Gas, treatment conditions are 200 DEG C, 0.1MPa, 100h^-1, time 4h.Catalyst is made, weight group becomes ZnBr₂Content is 5.2%, ZnO content 8.4%, Zr contents in terms of oxide are that 5%, Nd contents in terms of oxide are 5%.In catalyst 450 DEG C with Lower total acid content is 0.99mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 68.94% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Unstripped gas is a bromomethane, and reaction temperature is 270 DEG C, reaction pressure 2MPa（Absolute pressure）, air speed 350h^-1.It is passed through unstripped gas Before, catalyst activates under the mixed atmosphere of hydrogen, and hydrogen volume content is 60% in mixed gas, reducing condition 550 DEG C, 0.3MPa（Absolute pressure）, 800h^-1, recovery time 8h, it is halogen in reduction procatalyst to restore the content of halogen in rear catalyst The 40% of total content.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 94.86%, selective isobutene 82.21%.

Embodiment 6

In catalyst ratio zinc nitrate, zirconium nitrate, neodymium nitrate, aluminum nitrate is weighed to be added to the water, adjust solution ph be 2 ~ 3；Citric acid, return stirring 6 hours are added at 80 DEG C so that moisture is constantly evaporated up to form thick gel in solution, Gel aging 3 days at room temperature；The colloid is put into baking oven drying 12 hours at 120 DEG C, becomes dry glue shape；Then 350 It is roasted 8 hours at DEG C, catalyst precarsor ZnO-ZrO can be made₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, Catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 30% in monobromo methane blended gas, and surplus is nitrogen Gas, treatment conditions are 250 DEG C, 0.1MPa, 100h^-1, time 2h.Catalyst is made, weight group becomes ZnBr₂Content is 36.3%, ZnO content 2.8%, Zr contents in terms of oxide are that 5%, Nd contents in terms of oxide are 5%.In catalyst 450 DEG C with Lower total acid content is 1.03mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 69.67% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 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, reaction Pressure is 0.1MPa（Absolute pressure）, air speed 500h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixes It is 80% to close hydrogen volume content in gas, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, 1000h^-1, recovery time 4h, reduction Content of halogen in rear catalyst is restore total halogen content in procatalyst 56.46%.After stable reaction one hour, sampling Analysis.Bromomethane conversion ratio 99.38%, selective isobutene 75.05%.

Embodiment 7

In catalyst ratio zinc nitrate, zirconium nitrate, neodymium nitrate, aluminum nitrate is weighed to be added to the water, adjust solution ph be 2 ~ 3；Citric acid, return stirring 6 hours are added at 80 DEG C so that moisture is constantly evaporated up to form thick gel in solution, Gel aging 3 days at room temperature；The colloid is put into baking oven drying 12 hours at 120 DEG C, becomes dry glue shape；Then 350 It is roasted 8 hours at DEG C, catalyst precarsor ZnO-ZrO can be made₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, Catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 30% in monobromo methane blended gas, and surplus is nitrogen Gas, treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, time 4h.Catalyst is made, weight group becomes ZnBr₂Content is 31.2%, ZnO content 3.7%, Zr contents in terms of oxide are that 5%, Nd contents in terms of oxide are 5%.In catalyst 450 DEG C with Lower total acid content is 0.87mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 61.84% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 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, reaction Pressure is 3MPa（Absolute pressure）, air speed 350h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing Hydrogen volume content is 90% in gas, and reducing condition is 500 DEG C, 0.1MPa（Absolute pressure）, 500h^-1, recovery time 6h, after reduction Content of halogen in catalyst is restore total halogen content in procatalyst 50.22%.After stable reaction one hour, sampling point Analysis.Bromomethane conversion ratio 90.68%, selective isobutene 89.64%.

Embodiment 8

In catalyst ratio zinc nitrate, zirconium nitrate, neodymium nitrate, aluminum nitrate is weighed to be added to the water, adjust solution ph be 2 ~ 3；Citric acid, return stirring 6 hours are added at 80 DEG C so that moisture is constantly evaporated up to form thick gel in solution, Gel aging 3 days at room temperature；The colloid is put into baking oven drying 12 hours at 120 DEG C, becomes dry glue shape；Then 350 It is roasted 8 hours at DEG C, catalyst precarsor ZnO-ZrO can be made₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, Catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 30% in monobromo methane blended gas, and surplus is nitrogen Gas, treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, time 4h.Catalyst is made, weight group becomes ZnBr₂Content is 41.9%, ZnO content 6.2%, Zr contents in terms of oxide are that 5%, Nd contents in terms of oxide are 5%.In catalyst 450 DEG C with Lower total acid content is 0.9mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 53.51% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 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, reaction Pressure is 2MPa（Absolute pressure）, air speed 200h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa（Absolute pressure）, 800h^-1, recovery time 4h, after reduction Content of halogen in catalyst is restore total halogen content in procatalyst 37.84%.Bromomethane conversion ratio 98.84%, isobutyl Alkene selectivity 76.99%.

Embodiment 9

In catalyst ratio zinc nitrate, zirconium nitrate, neodymium nitrate, aluminum nitrate is weighed to be added to the water, adjust solution ph be 2 ~ 3；Citric acid, return stirring 6 hours are added at 80 DEG C so that moisture is constantly evaporated up to form thick gel in solution, Gel aging 3 days at room temperature；The colloid is put into baking oven drying 12 hours at 120 DEG C, becomes dry glue shape；Then 350 It is roasted 8 hours at DEG C, catalyst precarsor ZnO-ZrO can be made₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, Catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 30% in monobromo methane blended gas, and surplus is nitrogen Gas, treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, time 4h.Catalyst is made, weight group becomes ZnBr₂Content is 31.2%, ZnO content 3.7%, Zr contents in terms of oxide are that 5%, Nd contents in terms of oxide are 5%.In catalyst 450 DEG C with Lower total acid content is 0.85mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 57.82% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 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, reaction Pressure is 2MPa（Absolute pressure）, air speed 200h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa（Absolute pressure）, 800h^-1, recovery time 4h, after reduction Content of halogen in catalyst is restore total halogen content in procatalyst 61.62%.Bromomethane conversion ratio 99.80%, isobutyl Alkene selectivity 87.52%.

Embodiment 10

In catalyst ratio zinc nitrate, zirconium nitrate, neodymium nitrate, aluminum nitrate is weighed to be added to the water, adjust solution ph be 2 ~ 3；Citric acid, return stirring 6 hours are added at 80 DEG C so that moisture is constantly evaporated up to form thick gel in solution, Gel aging 3 days at room temperature；The colloid is put into baking oven drying 12 hours at 120 DEG C, becomes dry glue shape；Then 350 It is roasted 8 hours at DEG C, catalyst precarsor ZnO-ZrO can be made₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, Catalyst precarsor is handled under monobromo methane atmosphere, monobromo methane volumetric content is 30% in monobromo methane blended gas, and surplus is nitrogen Gas, treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, time 4h.Catalyst is made, weight group becomes ZnBr₂Content is 31.2%, ZnO content 3.7%, Zr contents in terms of oxide are that 5%, Nd contents in terms of oxide are 5%.In catalyst 450 DEG C with Lower total acid content is 1.05mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 61.57% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 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, reaction Pressure is 2MPa（Absolute pressure）, air speed 200h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa（Absolute pressure）, 800h^-1, recovery time 4h, after reduction Content of halogen in catalyst is restore total halogen content in procatalyst 60.64%.After stable reaction one hour, sampling point Analysis.Bromomethane conversion ratio 99.79%, selective isobutene 77.02%.

Embodiment 11

In catalyst ratio zinc nitrate, zirconium nitrate, neodymium nitrate, aluminum nitrate is weighed to be added to the water, adjust solution ph be 2 ~ 3；Citric acid, return stirring 6 hours are added at 80 DEG C so that moisture is constantly evaporated up to form thick gel in solution, Gel aging 3 days at room temperature；The colloid is put into baking oven drying 12 hours at 120 DEG C, becomes dry glue shape；Then 350 It is roasted 8 hours at DEG C, catalyst precarsor ZnO-ZrO can be made₂-CeO₂/Al₂O₃.Using continuous fixed bed reactor, Catalyst precarsor is handled under monobromo methane blended atmosphere, monobromo methane volumetric content is 30% in monobromo methane blended gas, processing Condition is 250 DEG C, 0.1MPa, 100h^-1, time 2h.Catalyst is made, weight group becomes ZnBr₂Content is 26.0%, ZnO It is 5%, Nd contents in terms of oxide is 5% that content, which is 4.7%, Zr contents in terms of oxide,.450 DEG C or less total acid contents in catalyst For 0.92mmol/g, 250 DEG C -350 DEG C of acid content accounts for the 57.63% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 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, reaction Pressure is 2MPa（Absolute pressure）, air speed 200h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa（Absolute pressure）, 800h^-1, recovery time 4h, after reduction Content of halogen in catalyst is restore total halogen content in procatalyst 51.85%.After stable reaction one hour, sampling point Analysis.Bromomethane conversion ratio 87.98%, selective isobutene 77.85%.

Comparative example 1

Catalyst preparation is the same as embodiment 5.Evaluating catalyst condition with embodiment 5, the difference is that, do not carry out at activation Reason.After reaction one hour, sampling analysis.Bromomethane conversion ratio 3.42%, selective isobutene 0.

Comparative example 2

Catalyst preparation with embodiment 5, the difference is that, do not carry out halogenation treatment.Evaluating catalyst condition is the same as implementation Example 5, after reacting one hour, sampling analysis.Bromomethane conversion ratio 90.68%, selective isobutene 0.

Comparative example 3

Catalyst preparation is the same as embodiment 5.Evaluating catalyst condition with embodiment 5, the difference is that, by zinc bromide whole It is reduced to zinc.After reaction one hour, sampling analysis.Bromomethane conversion ratio 1.64%, selective isobutene 0.

Claims (21)

1. a kind of halide preparing isobutene catalyst of additive modification, it is characterised in that：Zinc oxide weight in the catalyst Content is 0.5%-20%；Zinc halide weight content is 10%-50%；Zirconium oxide weight content is 0.1%-20%；Neodymia weight contains Amount is 0.1%-20%；Surplus is alumina catalyst support.

2. catalyst according to claim 1, it is characterised in that：Zinc oxide weight content is 1%- in the catalyst 15%；Zinc halide weight content is 15%-45%；Zirconium oxide weight content is 0.1%-15%；Neodymia weight content is 0.1%- 15%。

3. catalyst according to claim 1, it is characterised in that：Zinc oxide weight content is 1%-9% in the catalyst； Zinc halide weight content is 18%-39%；Zirconium oxide weight content is 0.5%-10%；Neodymia weight content is 0.5%-10%.

4. catalyst according to claim 1, it is characterised in that：450 DEG C or less total acid contents are 0.5mmol/ in catalyst g-1.3mmol/g；250 DEG C -350 DEG C of acid content accounts for the 20%-90% of 450 DEG C or less total acid contents.

5. catalyst according to claim 4, it is characterised in that：450 DEG C or less total acid contents are 0.6mmol/ in catalyst g-1.2mmol/g；250 DEG C -350 DEG C of acid content accounts for the 30%-80% of 450 DEG C or less total acid contents.

6. catalyst according to claim 5, it is characterised in that：450 DEG C or less total acid contents are 0.7mmol- in catalyst 1.1mmol/g；250 DEG C -350 DEG C of acid content accounts for the 40%-80% of 450 DEG C or less total acid contents.

7. the preparation method of catalyst described in claim 1, it is characterised in that：Include the following steps：

（1）Zinc salt, zirconates, neodymium salt and aluminium salt are dissolved in the water and are configured to the solution that pH value is 2 ~ 3；Add at 60 DEG C ~ 90 DEG C Enter complexing agent, return stirring 6h ~ 10h so that moisture is constantly evaporated up to form thick gel in solution, then carries out old Change；Gel after aging is become into dry glue shape by dry, catalyst precarsor can be made after fired；

（2）To step（1）The catalyst precarsor of gained carries out halogenation treatment, and halide preparing isobutene catalyst is made.

8. according to the method described in claim 7, it is characterized in that：Step（1）Middle zinc salt, zirconates, neodymium salt and aluminium salt are its nitre Hydrochlorate, sulfate or halide salt, complexing agent are citric acid, one kind in ethylene glycol or two kinds of mixing.

9. according to the method described in claim 7, it is characterized in that：Step（1）Middle aging temperature is 10 DEG C -90 DEG C, when aging Between be 1h-72h.

10. according to the method described in claim 7, it is characterized in that：Step（1）Middle drying temperature is 50 DEG C -200 DEG C；It is dry Time is 1h-48h；Calcination temperature is 200 DEG C -800 DEG C；Roasting time is 1h-24h.

11. according to the method described in claim 7, it is characterized in that：60 DEG C -150 DEG C of drying temperature；Drying time is 2h- 36h；Calcination temperature is 300 DEG C -600 DEG C；Roasting time is 2h-16h.

12. according to the method described in claim 7, it is characterized in that：Step（2）Middle halogenation treatment process is as follows：By step（1） Resulting material is placed in continuous fixed bed reactor, and 150 DEG C -400 DEG C are warming up under inert atmosphere；Then pass to halogenated first Alkane and inert gas gaseous mixture, halide volumn concentration is 1%-95% in gaseous mixture；Processing time is 0.5h-16h；Place Reason pressure is 0.1MPa-0.5MPa；Volume space velocity is 50h^-1-1000 h^-1。

13. according to the method for claim 12, it is characterised in that：180 DEG C -350 DEG C are warming up under inert atmosphere；Then lead to Enter halide and inert gas gaseous mixture, halide volumn concentration is 10%-90% in gaseous mixture；Processing time is 1h-8h；Processing pressure is 0.1MPa-0.3MPa；Volume space velocity is 100 h^-1-500 h^-1。

14. the application of catalyst described in claim 1, it is characterised in that：Using halide as raw material, reaction temperature be 150 DEG C- 350℃；Reaction pressure is 0.1MPa-5MPa；Air speed is 50h^-1-1000h^-1, need to carry out also original place to catalyst before charging Reason, it is the 20%-90% for restoring total halogen content in procatalyst to be restored to the content of halogen in catalyst.

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, need to carry out reduction treatment to catalyst before charging, be restored in catalyst Content of halogen be restore procatalyst in total halogen content 30%-80%.

16. application according to claim 14, it is characterised in that：Reduction treatment process is as follows：It will catalysis under inert atmosphere Agent is warming up to 300 DEG C -600 DEG C；It is 200h to then pass to air speed^-1-2000h^-1Hydrogen or hydrogen and inert gas gaseous mixture Body is down to reaction temperature and is passed through halide and reacted, in the gaseous mixture after 0.1MPa-0.5MPa handles 2h-16h Hydrogen volume percentage composition is 10%-95%.

17. application according to claim 16, it is characterised in that：By catalyzer temperature-elevating to 350 DEG C -550 under inert atmosphere ℃；It is 500h to then pass to air speed^-1-1000h^-1Hydrogen or hydrogen and inert gas mixed gas, in 0.1MPa- After 0.3MPa handles 4h-8h, it is down to reaction temperature and is passed through halide and reacted, hydrogen volume percentage contains in the gaseous mixture Amount is 30%-90%.

18. application according to claim 14, it is characterised in that：Raw material is the gaseous mixture of halide and inert gas Body, the volumetric concentration of halide is 10%-90% in mixed gas.

19. application according to claim 14, it is characterised in that：Halide is a halide, methylene halide, three One or more of halide.

20. application according to claim 19, it is characterised in that：Halide is a bromomethane, methylene bromide, tribromo first One or more of alkane.

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