CN106140213A - A kind of halide preparing isobutene catalyst of additive modification and its preparation method and application - Google Patents

Abstract

Present invention halide preparing isobutene catalyst disclosing a kind of additive modification and its preparation method and application。In described catalyst, zinc oxide weight content is 0.5%-20%；Zinc halide weight content is 10%-50%；Zirconium oxide weight content is 0.1%-20%；Dineodymium trioxide weight content is 0.1%-20%；Surplus is alumina catalyst support.Catalyst preparation process is as follows: (1) uses sol-gal process to prepare catalyst precarsor；(2) catalyst precarsor of step (1) gained is carried out halogenation treatment, prepare halide preparing isobutene catalyst.This catalyst can significantly improve the selectivity of isobutene..

Description

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

Technical field

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

Background technology

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

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

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

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

Summary of the invention

For the deficiencies in the prior art, present invention halide preparing isobutene catalyst that a kind of additive modification is provided and its preparation method and application

The halide preparing isobutene catalyst of a kind of additive modification, in described catalyst, zinc oxide weight content is 0.5%-20%, preferably 1%-15%, further preferred 1%-9%；Zinc halide weight content is 10%-50%, preferably 15%-45%, further preferred 18%-39%；Zirconium oxide weight content is 0.1%-20%, preferably 0.1%-15%, more preferably 0.5%-10%；Dineodymium trioxide weight content is 0.1%-20%, preferably 0.1%-15%, more preferably 0.5%-10%；Surplus is alumina catalyst support.

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

(1) zinc salt, zirconates, neodymium salt and aluminium salt are dissolved in the water it are configured to the solution that pH value is 2 ~ 3；Chelating agent, return stirring 6h ~ 10h so that in solution, moisture is constantly evaporated up to be formed thick gel, then carries out aging is added at 60 DEG C ~ 90 DEG C；Gel after aging is become dry glue shape through being dried, fired after can prepare catalyst precarsor；

(2) catalyst precarsor of step (1) gained is carried out halogenation treatment, prepare halide preparing isobutene catalyst.

In the inventive method step (1), described zinc salt, zirconates, neodymium salt and aluminium salt are its nitrate, sulfate or halide salt etc., preferably nitrate；Described chelating agent is the one in citric acid, ethylene glycol or two kinds of mixing, preferably citric acid.

The inventive method, the ageing process described in step (1) can be aged at room temperature, it is also possible to for aging under certain constant temperature, aging temperature is 10 DEG C-90 DEG C, preferably 50 DEG C-80 DEG C, and ageing time is 1h-72h, preferably 12h-48h.

The inventive method, also includes in step (1) being dried and roasting process.Baking temperature is 50 DEG C-200 DEG C, preferably 60 DEG C-150 DEG C, more preferably 100 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 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, in step (2), halogenation treatment process is as follows: be placed in continuous fixed bed reactor by step (1) gained material, is warming up to 150 DEG C-400 DEG C under inert atmosphere, preferably 180 DEG C-350 DEG C, more preferably 200 DEG C-300 DEG C；Then passing to halide and noble gas gaseous mixture, in gaseous mixture, halide volumn concentration is 1%-95%, preferably 10%-90%, and surplus is noble gas；The process time is 0.5h-16h, preferably 1h-8h, more preferably 1h-4h；Processing pressure is 0.1MPa-0.5MPa, preferably 0.1MPa-0.3MPa；Volume space velocity is 50h^-1-1000 h^-1, preferably 100 h^-1-500 h^-1。

The application of above-mentioned halide preparing isobutene catalyst, with halide as raw material, reaction temperature is 150 DEG C-350 DEG C, preferably 180 DEG C-300 DEG C, more preferably 200 DEG C-270 DEG C；Reaction pressure is 0.1MPa-5MPa, preferably 0.1MPa-3MPa；Air speed is 50h^-1-1000h^-1, preferably 200h^-1-500h^-1, needing before charging catalyst is carried out reduction treatment, the content of halogen being reduced in catalyst is the 20%-90%, preferably 30%-80%, further preferred 40%-80% of total halogen content in reduction procatalyst.

In above-mentioned application, a kind of concrete reduction treatment process is as follows: by catalyzer temperature-elevating to 300 DEG C-600 DEG C under inert atmosphere, preferably 350 DEG C-550 DEG C；Then passing to air speed is 200h^-1-2000h^-1, preferably 500h^-1-1000h^-1Hydrogen or the mixed gas of hydrogen and noble gas, at 0.1MPa-0.5MPa, after preferably 0.1MPa-0.3MPa processes 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.The present invention uses the preparation method of collosol and gel to improve the dispersibility of each component in catalyst, by the presoma of each component being dissolved in solvent in advance formation homogeneous phase solution, through solution reaction step, auxiliary agent, active metal and carrier can be made to realize the uniform mixing on molecular level in catalyst；Meanwhile, the method is used can also accurately to control the content of each component in catalyst.In catalyst prepared by sol-gal process, each component has higher dispersion, thus also improves the activity of catalyst, and the reaction converted at halide shows higher selective isobutene.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 by catalyst ratio, zirconium nitrate, neodymium nitrate, aluminum nitrate are added to the water, and regulation solution ph is 2；Citric acid, return stirring 6h so that in solution, moisture is constantly evaporated up to form thick gel, the most aging 3 days of gel is added at 70 DEG C；This colloid is put into baking oven be dried 24 hours at 80 DEG C, become dry glue shape；Then roasting 8 hours at 400 DEG C, can prepare catalyst precarsor ZnO-ZrO₂-Nd₂O₃/Al₂O₃.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 250 DEG C, 0.1MPa, 100h^-1, the time is 2h.Preparing catalyst, its weight consists of ZnBr₂Content is 27.7%, and ZnO content is 1.2%, and Zr content in terms of oxide is 5%, and Nd content in terms of oxide is 5%.In catalyst, less than 450 DEG C total acid contents are 0.78mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 60.82% 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 nitrogen mixed gas, and wherein monobromo methane volumetric content is 50%, and reaction temperature is 230 DEG C, and reaction pressure is 1MPa(absolute pressure), air speed is 500h^-1, it is passed through unstripped gas procatalyst and activates in a hydrogen atmosphere, reducing condition is 400 DEG C, 0.2MPa(absolute pressure), 1000h^-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 65.28%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 66.28%, selective isobutene 46.55%.

Embodiment 2

Weigh zinc nitrate by catalyst ratio, zirconium nitrate, neodymium nitrate, aluminum nitrate are added to the water, and regulation solution ph is 3；Citric acid, return stirring 8 hours so that in solution, moisture is constantly evaporated up to form thick gel, the most aging 3 days of gel is added at 80 DEG C；This colloid is put into baking oven be dried 16 hours at 100 DEG C, become dry glue shape；Then roasting 4 hours at 450 DEG C, can prepare catalyst precarsor ZnO-ZrO₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 50%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.2MPa, 200h^-1, the time is 4h.Preparing catalyst, its weight consists of ZnBr₂Content is 31.2%, and ZnO content is 3.7%, and Zr content in terms of oxide is 5%, and Nd content in terms of oxide is 5%.In catalyst, less than 450 DEG C total acid contents are 0.85mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 51.23% 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 87.23%, selective isobutene 62.59%.

Embodiment 3

Weigh zinc nitrate by catalyst ratio, zirconium nitrate, neodymium nitrate, aluminum nitrate are added to the water, and regulation solution ph is 2 ~ 3；Citric acid, return stirring 10 hours so that in solution, moisture is constantly evaporated up to form thick gel, the most aging 3 days of gel is added at 90 DEG C；This colloid is put into baking oven be dried 12 hours at 120 DEG C, become dry glue shape；Then roasting 8 hours at 350 DEG C, can prepare catalyst precarsor ZnO-ZrO₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 70%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, the time is 2h.Preparing catalyst, its weight consists of ZnBr₂Content is 6.9%, and ZnO content is 1.9%, and Zr content in terms of oxide is 5%, and Nd content in terms of oxide is 5%.In catalyst, less than 450 DEG C total acid contents are 0.71mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 65.31% 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 54.95%, selective isobutene 61.57%.

Embodiment 4

Weigh zinc nitrate by catalyst ratio, zirconium nitrate, neodymium nitrate, aluminum nitrate are added to the water, and regulation solution ph is 2 ~ 3；Citric acid, return stirring 6 hours so that in solution, moisture is constantly evaporated up to form thick gel, the most aging 3 days of gel is added at 80 DEG C；This colloid is put into baking oven be dried 12 hours at 120 DEG C, become dry glue shape；Then roasting 8 hours at 350 DEG C, can prepare catalyst precarsor ZnO-ZrO₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 50%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, the time is 2h.Preparing catalyst, its weight consists of ZnBr₂Content is 10.4%, and ZnO content is 7.5%, and Zr content in terms of oxide is 5%, and Nd content in terms of oxide is 5%.In catalyst, 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 39.91% of less than 450 DEG C total acid contents.

Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 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 89.66%, selective isobutene 82.08%.

Embodiment 5

Weigh zinc nitrate by catalyst ratio, zirconium nitrate, neodymium nitrate, aluminum nitrate are added to the water, and regulation solution ph is 2 ~ 3；Citric acid, return stirring 6 hours so that in solution, moisture is constantly evaporated up to form thick gel, the most aging 3 days of gel is added at 80 DEG C；This colloid is put into baking oven be dried 12 hours at 120 DEG C, become dry glue shape；Then roasting 8 hours at 350 DEG C, can prepare catalyst precarsor ZnO-ZrO₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 50%, and surplus is nitrogen, and treatment conditions are 200 DEG C, 0.1MPa, 100h^-1, the time is 4h.Preparing catalyst, its weight consists of ZnBr₂Content is 5.2%, and ZnO content is 8.4%, and Zr content in terms of oxide is 5%, and Nd content in terms of oxide is 5%.In catalyst, less than 450 DEG C total acid contents are 0.99mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 68.94% 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 94.86%, selective isobutene 82.21%.

Embodiment 6

Weigh zinc nitrate by catalyst ratio, zirconium nitrate, neodymium nitrate, aluminum nitrate are added to the water, and regulation solution ph is 2 ~ 3；Citric acid, return stirring 6 hours so that in solution, moisture is constantly evaporated up to form thick gel, the most aging 3 days of gel is added at 80 DEG C；This colloid is put into baking oven be dried 12 hours at 120 DEG C, become dry glue shape；Then roasting 8 hours at 350 DEG C, can prepare catalyst precarsor ZnO-ZrO₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 250 DEG C, 0.1MPa, 100h^-1, the time is 2h.Preparing catalyst, its weight consists of ZnBr₂Content is 36.3%, and ZnO content is 2.8%, and Zr content in terms of oxide is 5%, and Nd content in terms of oxide is 5%.In catalyst, less than 450 DEG C total acid contents are 1.03mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 69.67% 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 99.38%, selective isobutene 75.05%.

Embodiment 7

Weigh zinc nitrate by catalyst ratio, zirconium nitrate, neodymium nitrate, aluminum nitrate are added to the water, and regulation solution ph is 2 ~ 3；Citric acid, return stirring 6 hours so that in solution, moisture is constantly evaporated up to form thick gel, the most aging 3 days of gel is added at 80 DEG C；This colloid is put into baking oven be dried 12 hours at 120 DEG C, become dry glue shape；Then roasting 8 hours at 350 DEG C, can prepare catalyst precarsor ZnO-ZrO₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, the time is 4h.Preparing catalyst, its weight consists of ZnBr₂Content is 31.2%, and ZnO content is 3.7%, and Zr content in terms of oxide is 5%, and Nd content in terms of oxide is 5%.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 61.84% 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 90.68%, selective isobutene 89.64%.

Embodiment 8

Weigh zinc nitrate by catalyst ratio, zirconium nitrate, neodymium nitrate, aluminum nitrate are added to the water, and regulation solution ph is 2 ~ 3；Citric acid, return stirring 6 hours so that in solution, moisture is constantly evaporated up to form thick gel, the most aging 3 days of gel is added at 80 DEG C；This colloid is put into baking oven be dried 12 hours at 120 DEG C, become dry glue shape；Then roasting 8 hours at 350 DEG C, can prepare catalyst precarsor ZnO-ZrO₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, the time is 4h.Preparing catalyst, its weight consists of ZnBr₂Content is 41.9%, and ZnO content is 6.2%, and Zr content in terms of oxide is 5%, and Nd content in terms of oxide is 5%.In catalyst, less than 450 DEG C total acid contents are 0.9mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 53.51% 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%.Bromomethane conversion ratio 98.84%, selective isobutene 76.99%.

Embodiment 9

Weigh zinc nitrate by catalyst ratio, zirconium nitrate, neodymium nitrate, aluminum nitrate are added to the water, and regulation solution ph is 2 ~ 3；Citric acid, return stirring 6 hours so that in solution, moisture is constantly evaporated up to form thick gel, the most aging 3 days of gel is added at 80 DEG C；This colloid is put into baking oven be dried 12 hours at 120 DEG C, become dry glue shape；Then roasting 8 hours at 350 DEG C, can prepare catalyst precarsor ZnO-ZrO₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, the time is 4h.Preparing catalyst, its weight consists of ZnBr₂Content is 31.2%, and ZnO content is 3.7%, and Zr content in terms of oxide is 5%, and Nd content in terms of oxide is 5%.In catalyst, less than 450 DEG C total acid contents are 0.85mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 57.82% 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 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%.Bromomethane conversion ratio 99.80%, selective isobutene 87.52%.

Embodiment 10

Weigh zinc nitrate by catalyst ratio, zirconium nitrate, neodymium nitrate, aluminum nitrate are added to the water, and regulation solution ph is 2 ~ 3；Citric acid, return stirring 6 hours so that in solution, moisture is constantly evaporated up to form thick gel, the most aging 3 days of gel is added at 80 DEG C；This colloid is put into baking oven be dried 12 hours at 120 DEG C, become dry glue shape；Then roasting 8 hours at 350 DEG C, can prepare catalyst precarsor ZnO-ZrO₂-La₂O₃/Al₂O₃.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, the time is 4h.Preparing catalyst, its weight consists of ZnBr₂Content is 31.2%, and ZnO content is 3.7%, and Zr content in terms of oxide is 5%, and Nd content in terms of oxide is 5%.In catalyst, 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 61.57% 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.Bromomethane conversion ratio 99.79%, selective isobutene 77.02%.

Embodiment 11

Weigh zinc nitrate by catalyst ratio, zirconium nitrate, neodymium nitrate, aluminum nitrate are added to the water, and regulation solution ph is 2 ~ 3；Citric acid, return stirring 6 hours so that in solution, moisture is constantly evaporated up to form thick gel, the most aging 3 days of gel is added at 80 DEG C；This colloid is put into baking oven be dried 12 hours at 120 DEG C, become dry glue shape；Then roasting 8 hours at 350 DEG C, can prepare catalyst precarsor ZnO-ZrO₂-CeO₂/Al₂O₃.Using continuous fixed bed reactor, process catalyst precarsor under monobromo methane blended atmosphere, in monobromo methane blended gas, monobromo methane volumetric content is 30%, and treatment conditions are 250 DEG C, 0.1MPa, 100h^-1, the time is 2h.Preparing catalyst, its weight consists of ZnBr₂Content is 26.0%, and ZnO content is 4.7%, and Zr content in terms of oxide is 5%, and Nd content in terms of oxide is 5%.In catalyst, less than 450 DEG C total acid contents are 0.92mmol/g, and the acid content of 250 DEG C-350 DEG C accounts for the 57.63% of less than 450 DEG C total acid contents.

Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and 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 51.85%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio 87.98%, selective isobutene 77.85%.

Comparative example 1

Catalyst is prepared with embodiment 5.Evaluating catalyst condition is with embodiment 5, and difference is, does not carries out activation processing.After reacting one hour, sampling analysis.Bromomethane conversion ratio 3.42%, selective isobutene 0.

Comparative example 2

Catalyst is prepared with embodiment 5, and difference is, does not carries out halogenation treatment.Evaluating catalyst condition is with embodiment 5, after reacting one hour, and sampling analysis.Bromomethane conversion ratio 90.68%, selective isobutene 0.

Comparative example 3

Catalyst is prepared with embodiment 5.Evaluating catalyst condition is with embodiment 5, and difference is, is zinc by zinc bromide Restore All.After reacting one hour, sampling analysis.Bromomethane conversion ratio 1.64%, selective isobutene 0.

Claims (21)

1. the halide preparing isobutene catalyst of an additive modification, it is characterised in that: in described catalyst, zinc oxide weight content is 0.5%-20%；Zinc halide weight content is 10%-50%；Zirconium oxide weight content is 0.1%-20%；Dineodymium trioxide weight content is 0.1%-20%；Surplus is alumina catalyst support.

Catalyst the most according to claim 1, it is characterised in that: in described catalyst, zinc oxide weight content is 1%-15%；Zinc halide weight content is 15%-45%；Zirconium oxide weight content is 0.1%-15%；Dineodymium trioxide weight content is 0.1%-15%.

Catalyst the most according to claim 1, it is characterised in that: in described catalyst, zinc oxide weight content is 1%-9%；Zinc halide weight content is 18%-39%；Zirconium oxide weight content is 0.5%-10%；Dineodymium trioxide weight content is 0.5%-10%.

Catalyst the most according to claim 1, it is characterised in that: in catalyst, less than 450 DEG C total acid contents are 0.5mmol/g-1.3mmol/g；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；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；The acid content of 250 DEG C-350 DEG C accounts for the 40%-80% of less than 450 DEG C total acid contents.

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

(1) zinc salt, zirconates, neodymium salt and aluminium salt are dissolved in the water it are configured to the solution that pH value is 2 ~ 3；Chelating agent, return stirring 6h ~ 10h so that in solution, moisture is constantly evaporated up to be formed thick gel, then carries out aging is added at 60 DEG C ~ 90 DEG C；Gel after aging is become dry glue shape through being dried, fired after can prepare catalyst precarsor；

(2) catalyst precarsor of step (1) gained is carried out halogenation treatment, prepare halide preparing isobutene catalyst.

Method the most according to claim 7, it is characterised in that: in step (1), zinc salt, zirconates, neodymium salt and aluminium salt are its nitrate, sulfate or halide salt, and chelating agent is the one in citric acid, ethylene glycol or two kinds of mixing.

Method the most according to claim 7, it is characterised in that: in step (1), aging temperature is 10 DEG C-90 DEG C, and ageing time is 1h-72h.

Method the most according to claim 7, 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.

11. methods according to claim 7, it is characterised in that: baking temperature 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.

12. methods according to claim 7, it is characterised in that: in step (2), halogenation treatment process is as follows: is placed in continuous fixed bed reactor by step (1) gained 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。

13. methods according to claim 12, it is characterised in that: it is warming up to 180 DEG C-350 DEG C under inert atmosphere；Then passing to halide and noble gas gaseous mixture, 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。

The application of catalyst described in 14. claim 1, it is characterised in that: with halide as raw material, reaction temperature is 150 DEG C-350 DEG C；Reaction pressure is 0.1MPa-5MPa；Air speed is 50h^-1-1000h^-1, needing before charging catalyst is carried out reduction treatment, the content of halogen being reduced in catalyst is the 20%-90% of total halogen content in reduction procatalyst.

15. application according to claim 14, it is characterised in that: reaction temperature is 180 DEG C-300 DEG C；Reaction pressure is 0.1MPa-3MPa；Air speed is 200h^-1-500h^-1, 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.

16. application according to claim 14, it is characterised in that: reduction treatment process is as follows: by catalyzer temperature-elevating to 300 DEG C-600 DEG C under inert atmosphere；Then passing to air speed is 200h^-1-2000h^-1Hydrogen or the mixed gas of hydrogen and noble gas, 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%.

17. application according to claim 16, 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%.

18. application according to claim 14, 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%.

19. application according to claim 14, it is characterised in that: halide raw material is one or more in a halide, methylene halide, three halides.

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

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