CN106140218A

CN106140218A - A kind of loaded catalyst with meso-hole structure and its preparation method and application

Info

Publication number: CN106140218A
Application number: CN201510135820.6A
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: CN106140218B

Abstract

The present invention discloses a kind of loaded catalyst with meso-hole structure and its preparation method and application.Described catalyst is in terms of weight content, and zinc oxide content is 0.5%-20%；Zinc halide content is 10%-50%；Modified additive counts content as 0.1%-20% with oxide, and surplus is modified mesoporous alumina carrier.The preparation method of catalyst includes following process: (1) prepares modified mesoporous alumina carrier；(2) use the supported on carriers active metal zinc element presoma that incipient impregnation mode is prepared in step (1), after drying, roasting, prepare catalyst precarsor；(3) step (2) gained material is carried out halogenation treatment and prepare halide preparing isobutene catalyst.This catalyst can significantly improve the selectivity of isobutene. for the reaction of bromomethane preparing isobutene.

Description

A kind of loaded catalyst with meso-hole structure and its preparation method and application

Technical field

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

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

Summary of the invention

For the deficiencies in the prior art, the invention provides a kind of halide preparing isobutene catalyst with meso-hole structure and its preparation method and application.

A kind of halide preparing isobutene catalyst with meso-hole structure, 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%；Modified additive counts content as 0.1%-20% with oxide, preferably 0.1%-15%, more preferably 0.5%-5%, and surplus is modified mesoporous alumina carrier, and catalyst average pore size is 11nm ~ 16nm.Described zinc halide includes one or more in zinc fluoride, zinc chloride, zinc bromide, zinc iodide, preferably zinc bromide.

One or more in the metals such as one or more during auxiliary agent is the transition metals such as Ti, Zr, Ni, Co, Fe, Pt, Pd, Ru, Rh in described catalyst, preferably Ti, Zr, Pt, Pd；More preferably Zr.

The preparation method of above-mentioned catalyst, including following process: the modified mesoporous alumina carrier of (1) preparation；(2) use the supported on carriers active metal zinc element presoma that impregnation method is prepared in step (1), after drying, roasting, prepare catalyst precarsor；(3) step (2) gained material is carried out halogenation treatment；Prepare halide preparing isobutene catalyst.

The inventive method, in step (1), modified mesoporous alumina carrier uses in-situ synthesis to prepare, method particularly includes: template is dissolved in ethanol solution, add aluminum source and acid solution, 2h ~ 10h is stirred to dissolving completely at 20 DEG C ~ 60 DEG C, it is subsequently adding quantitative auxiliary agent presoma, after continuing stirring 2h ~ 10h, by gained material at 60 ~ 80 DEG C aging 1 day ~ 3 days, roasting 4h ~ 12h at 500 ~ 700 DEG C, can obtain the mesoporous alumina carrier of modification, the mol ratio that template, aluminum source, acid solution add is (0.01～0.7): 1:(3～70).

The inventive method, described in step (1), template is one or more in cetyl trimethylammonium bromide, Polyethylene Glycol, P123, F127, preferably P123；Template mass percentage concentration in ethanol is 1%-20%, preferably 1%-10%, more preferably 4%-8%.Source of aluminium is one or more in aluminum nitrate, aluminum sulfate, aluminum isopropylate., aluminum chloride, preferably one or more in aluminum isopropylate., aluminum nitrate, more preferably aluminum isopropylate.；Aluminum source mass percentage concentration in ethanol is 1%-20%, preferably 5%-20%, more preferably 8%-15%.Described acid solution is concentrated nitric acid, concentrated hydrochloric acid, citric acid, preferably concentrated nitric acid；Acid solution concentration expressed in percentage by volume in ethanol is 1%-20%, preferably 1%-15%, more preferably 3%-9%.

The inventive method, in step (2), active metal zinc element presoma is inorganic salt or organic salt, preferably nitrate, hydrochlorate, acetate, citrate, more preferably nitrate.

The inventive method, in step (2), baking temperature is 50 DEG C-200 DEG C, preferably 60 DEG C-150 DEG C, more preferably 80 DEG C-120 DEG C；Drying time is 1h-48h, preferably 2h-36h, more preferably 2h-24h；Can be vacuum drying time dry, it is also possible to for being dried under the conditions of inert gas shielding, it is also possible to be dried in air atmosphere；Sintering temperature is 200 DEG C-800 DEG C, preferably 300 DEG C-600 DEG C, more preferably 350 DEG C-500 DEG C；Roasting time is 1h-24h, preferably 2h-16h, more preferably 4h-8h；Can be to be dried under the conditions of inert gas shielding during roasting, it is also possible to be dried in air atmosphere.

The inventive method, in step (3), halogenation treatment process is as follows: be placed in continuous fixed bed reactor by step (2) 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(absolute pressure), preferably 0.1MPa-3MPa(absolute pressure)；Air speed is 50h^-1-1000h^-1, preferably 200h^-1-500h^-1, needing before charging catalyst is carried out reduction treatment, the content of halogen being reduced in catalyst is the 20%-90%, preferably 30%-80%, further preferred 40%-80% of total halogen content in reduction procatalyst.

In above-mentioned application, a kind of concrete reduction treatment process is as follows: by catalyzer temperature-elevating to 300 DEG C-600 DEG C under inert atmosphere, preferably 350 DEG C-550 DEG C；Then passing to air speed is 200h^-1-2000h^-1, preferably 500h^-1-1000h^-1Hydrogen or the mixed gas of hydrogen and noble gas, in 0.1MPa-0.5MPa(absolute pressure), preferably 0.1MPa-0.3MPa(absolute pressure) process 2h-16h, preferably 4h-8h after, be down to reaction temperature and be passed through halide and react.In described gaseous mixture, hydrogen volume percentage composition is 10%-95%, preferably 30%-90%, more preferably 50%-90%.

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

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

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

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

Compared with prior art, bromomethane height can be optionally converted into isobutene. by the method that the present invention relates to.Convert the needs of preparing isobutene reaction for adapting to halide, the present invention is prepared for the catalyst with meso-hole structure feature.The pore volume of this catalyst is bigger, it is possible to provide accommodate the reacting environment of halide preparing isobutene transition state species；Meanwhile, catalyst also has the aperture of 11nm ~ 16nm, can be that reactant and product molecule provide the passage being suitable to diffusion.The present invention, by adjusting pore volume and the aperture of catalyst, can improve selectivity of catalyst.And, additive modification is in terms of improving the structural stability of mesoporous alumina carrier and catalyst, it may have positive effect.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.

Embodiment 1

Measuring 100mL ethanol is solvent, adds 3.8g P123 stirring is allowed to dissolve, and weighs 9.6g aluminum isopropylate. and 5.4mL concentrated nitric acid and adds in solution, be stirred at room temperature to be dissolved after, add zirconium nitrate, at 30 DEG C, stir 8h；Gained sample is in 70 DEG C of aging 36h, at 650 DEG C of roasting 6h, can prepare modified meso-porous alumina.The preparation aqueous solution containing zinc nitrate, uses equi-volume impregnating to be carried on alumina support, and aged at room temperature 4h, 100 DEG C of dry 8h, 500 DEG C of roasting 4h prepare catalyst precarsor.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr₂Content is 30%, and ZnO content is 4%, ZrO₂Content is 4.5%.Use BET that catalyst is characterized, show that average pore size is 15.2nm.

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

Measuring 100mL ethanol is solvent, adds 4.1g P123 stirring is allowed to dissolve, and weighs 10g aluminum isopropylate. and 6.1mL concentrated nitric acid and adds in solution, be stirred at room temperature to be dissolved after, add zirconium nitrate, at 40 DEG C, stir 6h；Gained sample is in 60 DEG C of aging 48h, at 500 DEG C of roasting 10h, can prepare modified meso-porous alumina.The preparation aqueous solution containing zinc nitrate, uses equi-volume impregnating to be carried on alumina support, and aged at room temperature 4h, 100 DEG C of dry 8h, 500 DEG C of roasting 4h prepare catalyst precarsor.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr₂Content is 30%, and ZnO content is 4%, ZrO₂Content is 4.5%, and average pore size is 11.2nm.

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

Measuring 100mL ethanol is solvent, adds 4.6g P123 stirring is allowed to dissolve, and weighs 7.9g aluminum isopropylate. and 4.8mL concentrated nitric acid and adds in solution, be stirred at room temperature to be dissolved after, add zirconium nitrate, at 50 DEG C, stir 5h；Gained sample is in 70 DEG C of aging 48h, at 650 DEG C of roasting 6h, can prepare modified meso-porous alumina.The preparation aqueous solution containing zinc nitrate, uses equi-volume impregnating to be carried on alumina support, and aged at room temperature 4h, 100 DEG C of dry 8h, 500 DEG C of roasting 4h prepare catalyst precarsor.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr₂Content is 30%, and ZnO content is 4%, ZrO₂Content is 2%, and average pore size is 12.9nm.

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

Measuring 100mL ethanol is solvent, adds 5.2g P123 stirring is allowed to dissolve, and weighs 8.5g aluminum isopropylate. and 5.0mL concentrated nitric acid and adds in solution, be stirred at room temperature to be dissolved after, add zirconium nitrate, at 30 DEG C, stir 8h；Gained sample is in 60 DEG C of aging 36h, at 650 DEG C of roasting 6h, can prepare modified meso-porous alumina.The preparation aqueous solution containing zinc nitrate, uses equi-volume impregnating to be carried on alumina support, and aged at room temperature 4h, 100 DEG C of dry 8h, 500 DEG C of roasting 4h prepare catalyst precarsor.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr₂Content is 30%, and ZnO content is 4%, ZrO₂Content is 8.5%, and average pore size is 15.5nm.

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

Measuring 100mL ethanol is solvent, adds 3.0g P123 stirring is allowed to dissolve, and weighs 5.8g aluminum isopropylate. and 4.2mL concentrated nitric acid and adds in solution, be stirred at room temperature to be dissolved after, add zirconium nitrate, at 30 DEG C, stir 6h；Gained sample is in 60 DEG C of aging 36h, at 650 DEG C of roasting 6h, can prepare modified meso-porous alumina.The preparation aqueous solution containing zinc nitrate, uses equi-volume impregnating to be carried on alumina support, and aged at room temperature 4h, 100 DEG C of dry 8h, 500 DEG C of roasting 4h prepare catalyst precarsor.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr₂Content is 30%, and ZnO content is 4%, ZrO₂Content is 15%, and average pore size is 12.1nm.

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

Measuring 100mL ethanol is solvent, adds 3.9g P123 stirring is allowed to dissolve, and weighs 8.9g aluminum isopropylate. and 5.1mL concentrated nitric acid and adds in solution, be stirred at room temperature to be dissolved after, add zirconium nitrate, at 30 DEG C, stir 10h；Gained sample is in 70 DEG C of aging 36h, at 650 DEG C of roasting 6h, can prepare modified meso-porous alumina.The preparation aqueous solution containing zinc nitrate, uses equi-volume impregnating to be carried on alumina support, and aged at room temperature 4h, 100 DEG C of dry 8h, 500 DEG C of roasting 4h prepare catalyst precarsor.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr₂Content is 30%, and ZnO content is 4%, ZrO₂Content is 4.5%, and average pore size is 12.4nm.

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

Measuring 100mL ethanol is solvent, adds 4.2g P123 stirring is allowed to dissolve, and weighs 9.5g aluminum isopropylate. and 6.5mL concentrated nitric acid and adds in solution, be stirred at room temperature to be dissolved after, add zirconium nitrate, at 30 DEG C, stir 8h；Gained sample is in 70 DEG C of aging 36h, at 650 DEG C of roasting 6h, can prepare modified meso-porous alumina.The preparation aqueous solution containing zinc nitrate, uses equi-volume impregnating to be carried on alumina support, and aged at room temperature 4h, 100 DEG C of dry 8h, 500 DEG C of roasting 4h prepare catalyst precarsor.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr₂Content is 30%, and ZnO content is 4%, ZrO₂Content is 4.5%, and average pore size is 12.8nm.

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.

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. the preparation method of a loaded catalyst with meso-hole structure, it is characterised in that: comprise the steps:

(1) template is dissolved in ethanol solution, add aluminum source and acid solution, 2h ~ 10h is stirred to dissolving completely at 20 DEG C ~ 60 DEG C, it is subsequently adding auxiliary agent presoma, after continuing stirring 2h ~ 10h, by gained material at 60 ~ 80 DEG C aging 1 day ~ 3 days, at 500 ~ 700 DEG C, roasting 4h ~ 12h obtained modified mesoporous alumina carrier, and described template is one or more in cetyl trimethylammonium bromide, Polyethylene Glycol, P123, F127；Template mass percentage concentration in ethanol solution is 1%-20%, source of aluminium is one or more in aluminum nitrate, aluminum sulfate, aluminum isopropylate., aluminum chloride, described acid solution is one or more in concentrated nitric acid, concentrated hydrochloric acid, citric acid, and the mol ratio that template, aluminum source, acid solution add is (0.01～0.7): 1:(3～70).

2. auxiliary agent described in is one or more in Ti, Zr, Ni, Co, Fe, Pt, Pd, Ru, Rh, and promoter addition counts weight content in the catalyst as 0.1%-20% with oxide；

(2) use the supported on carriers active metal zinc element presoma that impregnation method is prepared in step (1), after drying, roasting, prepare catalyst precarsor；

(3) step (2) gained material being carried out halogenation treatment, halogenation to zinc halide weight content in the catalyst is 10%-50%, zinc oxide weight content is 0.5%-20%, prepares halide preparing isobutene catalyst, and catalyst average pore size is 11nm ~ 16nm.

Method the most according to claim 1, it is characterised in that: in step (1), template is P123；Template mass percentage concentration in ethanol solution is 1%-10%, aluminum source is one or more in aluminum isopropylate., aluminum nitrate, acid solution is concentrated nitric acid, and auxiliary agent is one or more in Ti, Zr, Pt, Pd, and auxiliary agent counts weight content in the catalyst as 0.1%-15% with oxide.

Method the most according to claim 2, it is characterised in that: in step (1), template mass percentage concentration in ethanol solution is 4%-8%, and aluminum source is aluminum isopropylate., and auxiliary agent is Zr, and auxiliary agent counts weight content in the catalyst as 0.5%-5% with oxide.

Method the most according to claim 1, it is characterised in that: in step (2), active metal zinc precursor is one or more in its nitrate, hydrochlorate, acetate, citrate.

Method the most according to claim 1, it is characterised in that: in step (2), baking temperature is 50 DEG C-200 DEG C；Drying time is 1h-48h；Sintering temperature is 200 DEG C-800 DEG C；Roasting time is 1h-24h.

Method the most according to claim 1, it is characterised in that: halogenation treatment described in step (3) uses gas phase halogen contained compound to process step (2) gained sample, and halogenation to zinc halide weight content in the catalyst is 15%-45%.

Method the most according to claim 6, it is characterised in that: halogen contained compound is one or more in a halide, methylene halide, three halides.

Method the most according to claim 6, 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%.

Method the most according to claim 1, it is characterized in that: halogenation process is as follows: the sample of step (2) 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.

11. methods according to claim 9, 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.

12. 1 kinds use catalyst prepared by claim 1 to 10 either method, it is characterised in that: based on the weight content of catalyst, zinc oxide content is 0.5%-20%；Zinc halide content is 10%-50%；Auxiliary agent counts content as 0.1%-20% with oxide；Described zinc halide includes one or more in zinc fluoride, zinc chloride, zinc bromide, zinc iodide, and auxiliary agent is one or more in Ti, Zr, Ni, Co, Fe, Pt, Pd, Ru, Rh, and catalyst average pore size is 11nm ~ 16nm,.

13. catalyst according to claim 11, it is characterised in that: content meter by weight, zinc oxide content is 1%-15%；Zinc halide content is 15%-45%；Auxiliary agent counts content as 0.1%-15% with oxide；Described zinc halide is zinc bromide, and auxiliary agent is one or more in Ti, Zr, Pt, Pd.

14. catalyst according to claim 12, it is characterised in that: content meter by weight, zinc oxide content is 1%-9%；Zinc halide content is 18%-39%；Auxiliary agent counts content as 0.5%-5% with oxide, and auxiliary agent is zirconium.

Catalyst application in preparing isobutene described in 15. claim 11, 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.

16. application according to claim 14, it is characterised in that: reaction temperature is 180 DEG C-300 DEG C；Reaction pressure is 0.1MPa-3MPa；Air speed is 200h^-1-500h^-1, the content of halogen being reduced in catalyst is the 30%-80% of total halogen content in reduction procatalyst.

17. application according to claim 14, it is characterised in that: reduction treatment process is as follows: by catalyzer temperature-elevating to 300 DEG C-600 DEG C under inert atmosphere；Then passing to air speed is 200h^-1-2000h^-1Hydrogen or the mixed gas of hydrogen and noble gas, process 2h-16h at 0.1MPa-0.5MPa, be down to reaction temperature and be passed through halide and react, in gaseous mixture, hydrogen volume percentage composition is 10%-95%.

18. application according to claim 16, it is characterised in that: it is warming up to 350 DEG C-550 DEG C；Then passing to air speed is 500h^-1-1000h^-1Hydrogen or the mixed gas of hydrogen and noble gas, process 4h-8h at 0.1MPa-0.3Mpa, in described gaseous mixture, hydrogen volume percentage composition is 30%-90%.

19. 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%.

20. application according to claim 18, it is characterised in that: noble gas is one or more in nitrogen, argon, helium.

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

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

22. application according to claim 14, 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.