CN106140218B - A kind of loaded catalyst and its preparation method and application with meso-hole structure - Google Patents

Abstract

The present invention discloses a kind of loaded catalyst and its preparation method and application with meso-hole structure.The catalyst is in terms of weight content, zinc oxide content 0.5%-20%；Halogenation Zn content is 10%-50%；Modified additive content in terms of oxide is 0.1%-20%, and surplus is modified mesoporous alumina carrier.The preparation method of catalyst comprises the following processes: (1) preparing modified mesoporous alumina carrier；(2) catalyst precarsor is made in the supported on carriers active metal Zn-ef ficiency presoma prepared using incipient impregnation mode in step (1) after drying, roasting；(3) halogenation treatment is carried out to step (2) resulting material and halide preparing isobutene catalyst is made.The catalyst can significantly improve the selectivity of isobutene for the reaction of bromomethane preparing isobutene.

Description

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

Technical field

The present invention relates to a kind of loaded catalyst and its preparation method and application with meso-hole structure, specifically relates to And a kind of halide preparing isobutene catalyst and its preparation method and application, there is meso-hole structure more specifically to one kind Halide preparing isobutene catalyst and its preparation method and application.

Background technique

Isobutene is a kind of important basic organic chemical industry raw material, and derived product is numerous, and vertical industry chain is complicated, is disappeared Take structure in diversified trend.A variety of high value-added products can be prepared by raw material of isobutene, such as: butyl rubber, gather it is 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 increasingly depleted in petroleum resources 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, one can prepare many chemical products 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 reacts the method for generating C3 ~ C13 mixing high-carbon hydrocarbon, and 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.(CN 102527427A, Jieli He, the Ting Xu, Zhihui such as Wang Ye 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 is the catalyst of appropriate microporous structure and acidity, which 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 dimethyl ether, methanol and metal bromide for bromo-hydrocarbons on metal oxide catalyst, and metal bromide is used Metal oxide is obtained after oxygen recovery and releases simple substance bromine, completes the circulation of bromine.

Currently, being mainly methanol and dimethyl ether about purpose product in the existing literature of halide conversion, in addition also 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.

Summary of the invention

In view of the deficiencies of the prior art, the halide preparing isobutene catalysis with meso-hole structure that the present invention provides a kind of Agent 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%；Halogenation Zn content be 10%-50%, preferably 15%-45%, into The preferred 18%-39% of one step；Modified additive content in terms of oxide is 0.1%-20%, preferably 0.1%-15%, further preferably 0.5%-5%, surplus are modified mesoporous alumina carrier, and catalyst average pore size is 11nm ~ 16nm.The zinc halide includes fluorination One or more of zinc, zinc chloride, zinc bromide, zinc iodide, preferably zinc bromide.

In the catalyst auxiliary agent be one of transition metal elements such as Ti, Zr, Ni, Co, Fe, Pt, Pd, Ru, Rh or It is several, preferably one or more of metals such as Ti, Zr, Pt, Pd；More preferably Zr.

The preparation method of above-mentioned catalyst, comprises the following processes: (1) preparing modified mesoporous alumina carrier；(2) using leaching The supported on carriers active metal Zn-ef ficiency presoma that stain mode is prepared in step (1), before catalyst is made after drying, roasting Body；(3) halogenation treatment is carried out to step (2) resulting material；Halide preparing isobutene catalyst is made.

The method of the present invention, in step (1) modified mesoporous alumina carrier using in-situ synthesis preparation, method particularly includes: Template is dissolved in ethanol solution, silicon source and acid solution is added, 2h ~ 10h is stirred at 20 DEG C ~ 60 DEG C and is extremely dissolved completely, so Quantitative auxiliary agent presoma is added afterwards, continue stir 2h ~ 10h after, by resulting material at 60 ~ 80 DEG C aging 1 day ~ 3 days, 4h ~ 12h is roasted at 500 ~ 700 DEG C, can be obtained modified mesoporous alumina carrier, mole that template, silicon source, acid solution are added Than for (0.01~0.7): 1:(3~70).

The method of the present invention, template described in step (1) be cetyl trimethylammonium bromide, polyethylene glycol, P123, One or more of F127, preferably P123；The mass percentage concentration of template in ethanol is 1%-20%, preferably 1%- 10%, more preferably 4%-8%.Source of aluminium be one or more of aluminum nitrate, aluminum sulfate, aluminium isopropoxide, aluminium chloride, preferably For one or more of aluminium isopropoxide, aluminum nitrate, more preferably aluminium isopropoxide；The mass percentage concentration of silicon source in ethanol is 1%-20%, preferably 5%-20%, more preferably 8%-15%.The acid solution be concentrated nitric acid, concentrated hydrochloric acid, citric acid, it is preferably dense Nitric acid；The concentration expressed in percentage by volume of acid solution in ethanol is 1%-20%, preferably 1%-15%, more preferably 3%-9%.

The method of the present invention, active metal Zn-ef ficiency presoma is inorganic salts or organic salt, preferably nitric acid in step (2) Salt, hydrochloride, acetate, citrate, more preferably nitrate.

The method of the present invention, drying temperature is 50 DEG C -200 DEG C in step (2), preferably 60 DEG C -150 DEG C, more preferably 80 ℃-120℃；Drying time is 1h-48h, preferably 2h-36h, more preferably 2h-24h；It can be vacuum drying when dry, It can be drying under the conditions of inert gas shielding, can also dry in air atmosphere；Maturing temperature is 200 DEG C -800 DEG C, excellent It is selected as 300 DEG C -600 DEG C, more preferably 350 DEG C -500 DEG C；Calcining time is 1h-24h, preferably 2h-16h, more preferably 4h- 8h；It can be drying under the conditions of inert gas shielding when roasting, can also dry in air atmosphere.

The method of the present invention, halogenation treatment process is as follows in step (3): it is solid that step (2) 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；The 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(absolute pressure), preferably 0.1MPa-3MPa(absolute pressure)；Air speed is 50h^-1-1000h^-1, preferably 200h^-1-500h^-1, need to carry out catalyst before charging Reduction treatment, being restored to the content of halogen in catalyst is the 20%-90%, preferably 30%- for restoring total halogen content in procatalyst 80%, further preferred 40%-80%.

In above-mentioned 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；Then passing to air speed is 200h^-1-2000h^-1, preferably 500h^-1-1000h^-1Hydrogen Or the mixed gas of hydrogen and inert gas, in 0.1MPa-0.5MPa(absolute pressure), preferably 0.1MPa-0.3MPa(absolute pressure) at 2h-16h is managed, after preferably 4h-8h, reaction temperature is down to and is passed through halide and reacted.Hydrogen volume in the gaseous mixture Percentage composition is 10%-95%, preferably 30%-90%, more preferably 50%-90%.

In above-mentioned 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%.

Inert gas involved in above-mentioned application is that nitrogen, argon gas, helium etc. are not sent out under the conditions of involved in the present invention The gas of biochemical reaction, 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 a bromomethane.

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

Compared with prior art, method of the present invention can by bromomethane it is highly selective be converted into isobutene.For The needs of halide conversion preparing isobutene reaction are adapted to, the present invention is prepared for the catalyst with meso-hole structure feature.This is urged The hole of agent holds larger, it is possible to provide accommodates the reacting environment of halide preparing isobutene transition state species；Meanwhile catalyst also has There is the aperture of 11nm ~ 16nm, the channel suitable for diffusion can be provided for reactants and products molecule.The present invention is by adjusting catalyst Kong Rong and aperture, the selectivity of catalyst can be improved.Moreover, additive modification is improving mesoporous alumina carrier and catalyst Structural stability in terms of, it may have positive effect.The present invention relates to bromomethanes to convert preparing isobutene catalyst preparation side Method is simple, is easy to industrialize.Bromomethane conversion preparing isobutene method of the present invention has reaction condition is mild, selectivity of product is high etc. Advantage, industrialization easy to accomplish, application prospect are boundless.

Specific embodiment

Technology contents and effect of the invention are further illustrated below with reference to embodiment, but do not limit the present invention.

Embodiment 1

Measurement 100mL ethyl alcohol is solvent, and 3.8g P123 stirring is added and is allowed to dissolve, weighs 9.6g aluminium isopropoxide and 5.4mL Concentrated nitric acid be added solution in, be stirred at room temperature it is to be dissolved after, be added zirconium nitrate, stir 8h at 30 DEG C；Gained sample is old in 70 DEG C Modified meso-porous alumina can be made in 650 DEG C of roasting 6h by changing 36h.The aqueous solution containing zinc nitrate is prepared, using isometric leaching Stain method is carried on alumina support, at room temperature aging 4h, 100 DEG C of dry 8h, 500 DEG C of roasting 4h, and catalyst precarsor is made.Make With continuous fixed bed reactor, catalyst precarsor is handled under mixed atmosphere, wherein monobromo methane volumetric content is 30%, Surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, time 4h.Halide preparing isobutene catalyst is made, In terms of weight content, ZnBr₂Content is 30%, ZnO content 4%, ZrO₂Content is 4.5%.Table is carried out to catalyst using BET Sign show that average pore size is 15.2nm.

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, restoring the content of halogen in rear catalyst is halogen in reduction procatalyst The 65.28% of plain total content.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.

Embodiment 2

Measurement 100mL ethyl alcohol is solvent, and 4.1g P123 stirring is added and is allowed to dissolve, weighs 10g aluminium isopropoxide and 6.1mL Concentrated nitric acid be added solution in, be stirred at room temperature it is to be dissolved after, be added zirconium nitrate, stir 6h at 40 DEG C；Gained sample is old in 60 DEG C Modified meso-porous alumina can be made in 500 DEG C of roasting 10h by changing 48h.The aqueous solution containing zinc nitrate is prepared, using isometric leaching Stain method is carried on alumina support, at room temperature aging 4h, 100 DEG C of dry 8h, 500 DEG C of roasting 4h, and catalyst precarsor is made.Make With continuous fixed bed reactor, catalyst precarsor is handled under mixed atmosphere, wherein monobromo methane volumetric content is 30%, Surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, time 4h.Halide preparing isobutene catalyst is made, In terms of weight content, ZnBr₂Content is 30%, ZnO content 4%, ZrO₂Content is 4.5%, average pore size 11.2nm.

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.Reaction result is shown in Table 1.

Embodiment 3

Measurement 100mL ethyl alcohol is solvent, and 4.6g P123 stirring is added and is allowed to dissolve, weighs 7.9g aluminium isopropoxide and 4.8mL Concentrated nitric acid be added solution in, be stirred at room temperature it is to be dissolved after, be added zirconium nitrate, stir 5h at 50 DEG C；Gained sample is old in 70 DEG C Modified meso-porous alumina can be made in 650 DEG C of roasting 6h by changing 48h.The aqueous solution containing zinc nitrate is prepared, using isometric leaching Stain method is carried on alumina support, at room temperature aging 4h, 100 DEG C of dry 8h, 500 DEG C of roasting 4h, and catalyst precarsor is made.Make With continuous fixed bed reactor, catalyst precarsor is handled under mixed atmosphere, wherein monobromo methane volumetric content is 30%, Surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, time 4h.Halide preparing isobutene catalyst is made, In terms of weight content, ZnBr₂Content is 30%, ZnO content 4%, ZrO₂Content is 2%, average pore size 12.9nm.

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.Reaction result is shown in Table 1.

Embodiment 4

Measurement 100mL ethyl alcohol is solvent, and 5.2g P123 stirring is added and is allowed to dissolve, weighs 8.5g aluminium isopropoxide and 5.0mL Concentrated nitric acid be added solution in, be stirred at room temperature it is to be dissolved after, be added zirconium nitrate, stir 8h at 30 DEG C；Gained sample is old in 60 DEG C Modified meso-porous alumina can be made in 650 DEG C of roasting 6h by changing 36h.The aqueous solution containing zinc nitrate is prepared, using isometric leaching Stain method is carried on alumina support, at room temperature aging 4h, 100 DEG C of dry 8h, 500 DEG C of roasting 4h, and catalyst precarsor is made.Make With continuous fixed bed reactor, catalyst precarsor is handled under mixed atmosphere, wherein monobromo methane volumetric content is 30%, Surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, time 4h.Halide preparing isobutene catalyst is made, In terms of weight content, ZnBr₂Content is 30%, ZnO content 4%, ZrO₂Content is 8.5%, average pore size 15.5nm.

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.Reaction result is shown in Table 1.

Embodiment 5

Measurement 100mL ethyl alcohol is solvent, and 3.0g P123 stirring is added and is allowed to dissolve, weighs 5.8g aluminium isopropoxide and 4.2mL Concentrated nitric acid be added solution in, be stirred at room temperature it is to be dissolved after, be added zirconium nitrate, stir 6h at 30 DEG C；Gained sample is old in 60 DEG C Modified meso-porous alumina can be made in 650 DEG C of roasting 6h by changing 36h.The aqueous solution containing zinc nitrate is prepared, using isometric leaching Stain method is carried on alumina support, at room temperature aging 4h, 100 DEG C of dry 8h, 500 DEG C of roasting 4h, and catalyst precarsor is made.Make With continuous fixed bed reactor, catalyst precarsor is handled under mixed atmosphere, wherein monobromo methane volumetric content is 30%, Surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, time 4h.Halide preparing isobutene catalyst is made, In terms of weight content, ZnBr₂Content is 30%, ZnO content 4%, ZrO₂Content is 15%, average pore size 12.1nm.

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, and reaction pressure is 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, restoring the content of halogen in rear catalyst is halogen in reduction procatalyst The 40% of total content.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.

Embodiment 6

Measurement 100mL ethyl alcohol is solvent, and 3.9g P123 stirring is added and is allowed to dissolve, weighs 8.9g aluminium isopropoxide and 5.1mL Concentrated nitric acid be added solution in, be stirred at room temperature it is to be dissolved after, be added zirconium nitrate, stir 10h at 30 DEG C；Gained sample is old in 70 DEG C Modified meso-porous alumina can be made in 650 DEG C of roasting 6h by changing 36h.The aqueous solution containing zinc nitrate is prepared, using isometric leaching Stain method is carried on alumina support, at room temperature aging 4h, 100 DEG C of dry 8h, 500 DEG C of roasting 4h, and catalyst precarsor is made.Make With continuous fixed bed reactor, catalyst precarsor is handled under mixed atmosphere, wherein monobromo methane volumetric content is 30%, Surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, time 4h.Halide preparing isobutene catalyst is made, In terms of weight content, ZnBr₂Content is 30%, ZnO content 4%, ZrO₂Content is 4.5%, average pore size 12.4nm.

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 Closing hydrogen volume content in gas is 80%, 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.Reaction result is shown in Table 1.

Embodiment 7

Measurement 100mL ethyl alcohol is solvent, and 4.2g P123 stirring is added and is allowed to dissolve, weighs 9.5g aluminium isopropoxide and 6.5mL Concentrated nitric acid be added solution in, be stirred at room temperature it is to be dissolved after, be added zirconium nitrate, stir 8h at 30 DEG C；Gained sample is old in 70 DEG C Modified meso-porous alumina can be made in 650 DEG C of roasting 6h by changing 36h.The aqueous solution containing zinc nitrate is prepared, using isometric leaching Stain method is carried on alumina support, at room temperature aging 4h, 100 DEG C of dry 8h, 500 DEG C of roasting 4h, and catalyst precarsor is made.Make With continuous fixed bed reactor, catalyst precarsor is handled under mixed atmosphere, wherein monobromo methane volumetric content is 30%, Surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h^-1, time 4h.Halide preparing isobutene catalyst is made, In terms of weight content, ZnBr₂Content is 30%, ZnO content 4%, ZrO₂Content is 4.5%, average pore size 12.8nm.

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.Reaction result is shown in Table 1.

Comparative example 1

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

Comparative example 2

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

Comparative example 3

With embodiment 1, all it is reduced to the difference is that being activated completely during preparing isobutene even if zinc bromide Zinc.Reaction result is shown in Table 1.

Table 1

Claims (22)

1. a kind of preparation method of the loaded catalyst with meso-hole structure, characterized by the following steps:

(1) template is dissolved in ethanol solution, silicon source and acid solution is added, 2h ~ 10h is stirred at 20 DEG C ~ 60 DEG C to dissolution Completely, then be added auxiliary agent presoma, continue stir 2h ~ 10h after, by resulting material at 60 ~ 80 DEG C aging 1 day ~ 3 days, 4h ~ 12h is roasted at 500 ~ 700 DEG C and obtains modified mesoporous alumina carrier, and the template is cetyl trimethyl bromination One or more of ammonium, polyethylene glycol, P123, F127；Mass percentage concentration of the template in ethanol solution is 1%-20%, Source of aluminium is one or more of aluminum nitrate, aluminum sulfate, aluminium isopropoxide, aluminium chloride, and the acid solution is concentrated nitric acid, dense salt One or more of acid, citric acid, the molar ratio that template, silicon source, acid solution are added are (0.01~0.7): 1:(3~70)；

The auxiliary agent is one or more of Ti, Zr, Ni, Co, Fe, Pt, Pd, Ru, Rh, promoter addition in terms of oxide Weight content in catalyst is 0.1%-20%；

(2) the supported on carriers active metal Zn-ef ficiency presoma prepared using impregnation method in step (1), through drying, roasting Catalyst precarsor is made afterwards；

(3) halogenation treatment is carried out to step (2) resulting material, the weight content of halogenation to zinc halide in the catalyst is 10%- 50%, zinc oxide weight content be 0.5%-20%, be made halide preparing isobutene catalyst, catalyst average pore size be 11nm ~ 16nm。

2. according to the method described in claim 1, it is characterized by: template is P123 in step (1)；Template is molten in ethyl alcohol Mass percentage concentration in liquid is 1%-10%, and silicon source is one or more of aluminium isopropoxide, aluminum nitrate, and acid solution is concentrated nitric acid, Auxiliary agent is one or more of Ti, Zr, Pt, Pd, and weight content of the auxiliary agent in terms of oxide in the catalyst is 0.1%-15%.

3. according to the method described in claim 2, it is characterized by: quality hundred of the template in ethanol solution in step (1) Point concentration is 4%-8%, and silicon source is aluminium isopropoxide, auxiliary agent Zr, and weight content of the auxiliary agent in terms of oxide in the catalyst is 0.5%-5%。

4. according to the method described in claim 1, it is characterized by: in step (2) active metal zinc precursor be its nitrate, One or more of hydrochloride, acetate, citrate.

5. according to the method described in claim 1, it is characterized by: drying temperature is 50 DEG C -200 DEG C in step (2)；When dry Between be 1h-48h；Maturing temperature is 200 DEG C -800 DEG C；Calcining time is 1h-24h.

6. according to the method described in claim 1, it is characterized by: halogenation treatment described in step (3) contains halogen using gas phase Compound handles sample obtained by step (2), and the weight content of halogenation to zinc halide in the catalyst is 15%-45%.

7. according to the method described in claim 6, it is characterized by: halogen contained compound be a halide, methylene halide, One or more of three halides.

8. according to the method described in claim 6, it is characterized by: using gas phase halogen contained compound and inert gas mixing Gas carries out halogenation treatment, and halide volumetric concentration is not less than 20%.

9. according to the method described in claim 1, it is characterized by: halogenation process is as follows: the sample of step (2) is placed in continuously It flows in fixed bed reactors, 150 DEG C -400 DEG C is warming up under inert atmosphere, is passed through gas phase halogen contained compound gas, gas Air speed is 50h^-1-1000 h^-1；It is carried out when processing in normal pressure or under the conditions of pressure is 0.1MPa-0.5MPa, handles the time For 0.5h-8h.

10. according to the method described in claim 9, it is characterized by: be warming up to 180 DEG C -350 DEG C under inert atmosphere, gas space Speed is 100h^-1-500h^-1；System pressure is 0.1MPa-0.3MPa, and the processing time is 1h-4h.

11. a kind of catalyst prepared using claims 1 to 10 either method, it is characterised in that: contain by the weight of catalyst Meter, zinc oxide content 0.5%-20%；Halogenation Zn content is 10%-50%；Auxiliary agent content in terms of oxide is 0.1%-20%；Institute Stating zinc halide includes one or more of zinc fluoride, zinc chloride, zinc bromide, zinc iodide, auxiliary agent Ti, Zr, Ni, Co, Fe, One or more of Pt, Pd, Ru, Rh, catalyst average pore size are 11nm ~ 16nm.

12. catalyst according to claim 11, it is characterised in that: content meter by weight, zinc oxide content 1%-15%； Halogenation Zn content is 15%-45%；Auxiliary agent content in terms of oxide is 0.1%-15%；The zinc halide be zinc bromide, auxiliary agent Ti, One or more of Zr, Pt, Pd.

13. catalyst according to claim 12, it is characterised in that: content meter by weight, zinc oxide content 1%-9%； Halogenation Zn content is 18%-39%；Auxiliary agent content in terms of oxide is 0.5%-5%, and auxiliary agent is zirconium.

14. application of the catalyst described in claim 11 in preparing isobutene, it is characterised in that: using halide as raw material, instead Answering temperature is 150 DEG C -350 DEG C；Reaction pressure is 0.1MPa-5MPa；Air speed is 50h^-1-1000h^-1, need before charging to catalysis Agent carries out reduction treatment, and being restored to the content of halogen in catalyst is the 20%-90% for restoring total halogen content in 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, it is total for halogen in reduction procatalyst to be restored to the content of halogen in catalyst The 30%-80% of content.

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

17. application according to claim 16, it is characterised in that: be warming up to 350 DEG C -550 DEG C；Then passing to air speed is 500h^-1-1000h^-1Hydrogen or hydrogen and inert gas mixed gas, handle 4h-8h in 0.1MPa-0.3Mpa, it is described mixed Closing hydrogen volume percentage composition in gas 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 18, it is characterised in that: inert gas is one or more of argon gas, helium.

20. application according to claim 14, it is characterised in that: halide raw material is a halide, dihalo first Alkane, three halides.

21. application according to claim 20, it is characterised in that: halide raw material is a bromomethane, methylene bromide, three One or more of bromomethane.

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