CN106140216B - A kind of P Modification halide preparing isobutene catalyst and preparation method thereof - Google Patents

Abstract

The present invention discloses a kind of P Modification halide preparing isobutene catalyst and preparation method thereof.Catalyst content meter by weight, zinc oxide content are 0.5% 20%；Halogenation Zn content is 10% 50%；The weight content of phosphorus based on the element in the catalyst is 0.1% 20%.Catalyst preparation comprises the following processes：（1）First P elements presoma is carried on alumina support using step impregnation method, P Modification aluminium oxide is made after drying, roasting；Zinc supported elemental precursor is then proceeded to, catalyst precarsor can be made after drying, roasting；（2）To step（1）Gained catalyst precarsor, which carries out halogenation treatment, can be made halide preparing isobutene catalyst.The catalyst can prepare highly selective isobutene.

Description

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

Technical field

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

Background technology

Isobutene is a kind of important basic organic chemical industry raw material, and derived product is numerous, and vertical industry chain is complicated, consumption Structure is in diversified trend.A variety of high value-added products can be prepared by raw material of isobutene, such as：Butyl rubber, polyisobutene, A variety of Organic Chemicals such as methyl tertiary butyl ether(MTBE), isoprene and organic glass and fine chemistry product.Due under isobutene The market scale of trip product constantly expands, and imbalance between supply and demand will be protruded gradually, especially the background in petroleum resources increasingly depleted Under, isobutene yield has become the critical bottleneck for restricting downstream industry development.Therefore, the isobutene for developing non-petroleum base prepares road Line, it is extremely urgent.

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

Bromomethane is important methane halides, and one many chemical products can be prepared from bromomethane.Chinese patent CN 101041609A, CN 101284232A disclose it is a kind of by methane in oxygen and HBr/H₂Bromo first is converted under the action of O Alkane, then bromomethane further react the method for generating C3 ~ C13 mixing high-carbon hydrocarbons, the hydrocarbon selective of C5 or more is 70%. Wherein, HBr is used for methane bromination in first reactor, then discharges in second reactor, is used further to after recovered In back reaction, the recycling of HBr is realized.Wang Ye etc.（CN 102527427A, Jieli He, Ting Xu, Zhihui Wang, et.al. Angew. Chem. Int. Ed. 2012, 51, 2438-2442）Disclose a kind of halide system third Modified molecular sieve catalyst of alkene and preparation method thereof.By using fluorochemical moditied processing molecular sieve, obtains one kind and contain There are the catalyst of appropriate microporous structure and acidity, the catalyst that can effectively be catalyzed the reaction that halide is converted into propylene. Prepared catalyst one way bromomethane conversion ratio in the preparing propylene transformed reaction of bromomethane is 35 ~ 99%, the selectivity of propylene It is 27 ~ 70%；One way methyl chloride conversion rate is 30 ~ 99% in the preparing propylene transformed reaction of chloromethanes, the selectivity of propylene is 15 ~ 70%.Ivan M. Lorkovic et al.（Ivan M. Lorkovic, Aysen Yilmaz, Gurkan A. Yilmaz, et al. Catalysis Today, 2004, 98, 317-322）It is also proposed that generating bromo with the alkane reaction in bromine and natural gas Hydrocarbon, then converts bromo-hydrocarbons to dimethyl ether, methanol and metal bromide on metal oxide catalyst, and metal bromide is used Metal oxide is obtained after oxygen recovery and releases simple substance bromine, completes the cycle of bromine.

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

Invention content

It is an advantage of the invention to provide a kind of catalyst of P Modification halide preparing isobutene.The present invention's Another purpose is, provides the preparation method of above-mentioned catalyst.

A kind of halide preparing isobutene catalyst, it is characterised in that：Based on the weight content of catalyst, zinc oxide content For 0.5%-20%, preferably 1%-15%, further preferred 1%-9%；Halogenation Zn content be 10%-50%, preferably 15%-45%, further It is preferred that 18%-39%；Vector contg 40%-90%, preferably 50%-85%, further preferred 55%-80%；The zinc halide includes fluorination One or more of zinc, zinc chloride, zinc bromide, zinc iodide, preferably zinc bromide；The carrier is aluminium oxide.

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

Based on the element, mass percent in the catalyst is 0.1%-20%, preferably 0.1%-15% to the auxiliary agent phosphorus, more Preferably 0.5%-10%.

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

（1）First P elements presoma is carried on alumina support using infusion process, phosphorus is made after drying, roasting and changes Property aluminium oxide；Zinc supported elemental precursor is then proceeded to, catalyst precarsor can be made after drying, roasting；

（2）To step（1）Gained catalyst precarsor carries out halogenation treatment；Halide preparing isobutene catalyst can be made.

The method of the present invention, step（1）Described in Zn-ef ficiency presoma be inorganic salts or organic salt, preferably zinc nitrate, chlorine Change zinc, zinc acetate, more preferably zinc nitrate.

The method of the present invention, step（1）Described in P elements presoma be oxide, halide, oxyhalide, phosphoric acid, It is one or more in the forms such as phosphate, preferably phosphoric acid.

Catalyst carrier of the present invention can be by it is well known that prepared by method.The present invention relates to catalyst can root It needs to be made suitable particle shape according to what is used, such as bar shaped, piece shape, cylindricality, spherical shape is made.Forming can be by this field one As knowledge carry out.

The method of the present invention, step（1）Described in drying temperature be 50 DEG C -200 DEG C, preferably 60 DEG C -150 DEG C, more preferably It is 80 DEG C -120 DEG C；Drying time is 1h-24h, preferably 4h-8h；It can be vacuum drying when dry, or indifferent gas It is dry under body protective condition, it can also dry in air atmosphere.

The method of the present invention, step（1）Described in calcination temperature be 200 DEG C -800 DEG C, preferably 400 DEG C -600 DEG C；Roasting Time is 1h-24h, preferably 4h-8h；It can be to be roasted under the conditions of inert gas shielding when roasting, it can also be in air atmosphere Lower roasting.

The method of the present invention, step（2）Described in halogenation treatment, refer to using gas phase halogen contained compound to load zinc oxide Sample handled.Halogen contained compound refers to a halide, methylene halide, one kind in three halides or several Kind, a preferably halide, more preferably a bromomethane.The mixed of gas phase halogen contained compound and inert gas can also be used It closes gas and carries out halogenation treatment, when using mixed gas halogenation treatment, halide volumetric concentration is not less than 20%, preferably not Less than 30%.Specific halogenation process is as follows：The sample for loading zinc oxide is placed in continuous fixed bed reactor, indifferent gas It is warming up to 150 DEG C -400 DEG C, preferably 180 DEG C -350 DEG C, more preferably 200 DEG C -300 DEG C under atmosphere, is passed through gas phase containing halogenated Close object gas, gas space velocity 50h^-1-1000 h^-1, preferably 100h^-1-500h^-1；It can carry out in normal pressure when processing, also may be used To carry out under a certain pressure, system pressure 0.1MPa-0.5MPa, preferably 0.1MPa-0.3MPa, processing time is 0.5h-8h, preferably 1h-4h.

The application of above-mentioned halide preparing isobutene catalyst, using halide as raw material, reaction temperature is 150 DEG C -350 DEG C, preferably 180 DEG C -300 DEG C, more preferably 200 DEG C -270 DEG C；Reaction pressure is 0.1MPa-5MPa, preferably 0.1MPa- 3MPa；Air speed is 50h^-1-1000h^-1, preferably 200h^-1-500h^-1, need to carry out activation process, activation to catalyst before charging It is 20%-90%, the preferably 30%-80% for restoring total halogen content in procatalyst to the content of halogen in catalyst, it is further excellent Select 40%-80%.

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

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

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

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

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

Compared with prior art, method of the present invention can by bromomethane it is highly selective be converted into isobutene.It presses The method of the present invention can improve the acidic site of catalyst surface using P Modification, and suitable acid site is provided for the conversion of bromomethane. The present invention relates to bromomethane conversion preparing isobutene method for preparing catalyst it is simple, be easy to industrialize.Bromomethane conversion system of the present invention Isobutene method has many advantages, such as that reaction condition is mild, selectivity of product is high, industrialization easy to implement, and application prospect is very wide It is wealthy.

Specific implementation mode

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

Embodiment 1

It weighs appropriate phosphoric acid to be dissolved in deionized water, be carried on alumina support using equi-volume impregnating, 120 DEG C Dry 4h, 350 DEG C of roasting 8h, is made P Modification alumina support.Then it weighs appropriate zinc nitrate to be dissolved in deionized water, use Equi-volume impregnating is carried on P Modification alumina support, 80 DEG C of dry 8h, and catalyst precarsor is made in 600 DEG C of roasting 4h ZnO-P/Al₂O₃.5g catalyst precarsors are placed in continuous fixed bed reactor, before handling catalyst using a bromomethane Body, treatment conditions are：230 DEG C, 0.1MPa, 100h^-1, time 4h.Halide preparing isobutene catalyst is made, is denoted as C- 01.Catalyst weight group becomes ZnBr₂It is 3.7%, P weight contents is 3% that weight content, which is 31.3%, ZnO weight contents,.Catalysis 450 DEG C or less total acid contents are 0.85mmol/g in agent C-01, and 250 DEG C -350 DEG C of acid content accounts for 450 DEG C or less total acid contents 62.33%。

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 50%, and reaction temperature is 230 DEG C, reaction Pressure is 1MPa（Absolute pressure）, air speed 500h^-1, it is passed through unstripped gas procatalyst and activates in a hydrogen atmosphere, reducing condition 400 DEG C, 0.2MPa（Absolute pressure）, 1000h^-1, recovery time 4h, it is halogen in reduction procatalyst to restore the content of halogen in rear catalyst The 65.28% of plain total content.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.

Embodiment 2

With embodiment 1, obtained catalyst is denoted as C-02, the difference is that, catalyst weight group becomes ZnBr₂Weight contains It is 1.2%, P weight contents is 3% that amount, which is 10.4%, ZnO weight contents,.450 DEG C or less total acid contents are in catalyst C-02 0.68mmol/g, 250 DEG C -350 DEG C of acid content account for the 49.86% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, reaction Pressure is 2MPa（Absolute pressure）, air speed 200h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa（Absolute pressure）, 800h^-1, recovery time 4h, after reduction Content of halogen in catalyst is restore total halogen content in procatalyst 51.7%.After stable reaction one hour, sampling point Analysis.Reaction result is shown in Table 1.

Embodiment 3

With embodiment 1, obtained catalyst is denoted as C-03, the difference is that, catalyst weight group becomes ZnBr₂Weight contains It is 7.8%, P weight contents is 3% that amount, which is 43.3%, ZnO weight contents,.450 DEG C or less total acid contents are in catalyst C-03 0.89mmol/g, 250 DEG C -350 DEG C of acid content account for the 66.56% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 80%, and reaction temperature is 200 DEG C, reaction Pressure is 3MPa（Absolute pressure）, air speed 350h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing Hydrogen volume content is 50% in gas, and reducing condition is 500 DEG C, 0.1MPa（Absolute pressure）, 500h^-1, recovery time 4h, after reduction Content of halogen in catalyst is restore total halogen content in procatalyst 45.66%.After stable reaction one hour, sampling point Analysis.Reaction result is shown in Table 1.

Embodiment 4

With embodiment 1, obtained catalyst is denoted as C-04, the difference is that, catalyst weight group becomes ZnBr₂Weight contains It is 3.8%, P weight contents is 1% that amount, which is 30.6%, ZnO weight contents,.Reaction condition is the same as embodiment 1.450 DEG C in catalyst C-04 Following total acid content is 0.61mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 45.62% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 30%, and reaction temperature is 270 DEG C, reaction Pressure is 2MPa（Absolute pressure）, air speed 350h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing Hydrogen volume content is 70% in gas, and reducing condition is 350 DEG C, 0.3MPa（Absolute pressure）, 800h^-1, recovery time 6h, after reduction Content of halogen in catalyst is restore total halogen content in procatalyst 55.9%.After stable reaction one hour, sampling point Analysis.Reaction result is shown in Table 1.

Embodiment 5

With embodiment 1, obtained catalyst is denoted as C-05, the difference is that, catalyst weight group becomes ZnBr₂Weight contains It is 3.6%, P weight contents is 6% that amount, which is 31.5%, ZnO weight contents,.Reaction condition is the same as embodiment 1.450 DEG C in catalyst C-05 Following total acid content is 0.73mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 54.59% of 450 DEG C or less total acid contents.

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

Embodiment 6

With embodiment 1, obtained catalyst is denoted as C-06, the difference is that, catalyst weight group becomes ZnBr₂Weight contains It is 4.0%, P weight contents is 10% that amount, which is 29.6%, ZnO weight contents,.Reaction condition is the same as embodiment 1.450 in catalyst C-06 DEG C or less total acid content be 1.02mmol/g, 250 DEG C -350 DEG C of acid content accounts for the 76.28% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 50%, and reaction temperature is 230 DEG C, reaction Pressure is 0.1MPa（Absolute pressure）, air speed 500h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixes It is 80% to close hydrogen volume content in gas, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, 1000h^-1, recovery time 4h, reduction Content of halogen in rear catalyst is restore total halogen content in procatalyst 56.46%.After stable reaction one hour, sampling Analysis.Reaction result is shown in Table 1.

Embodiment 7

With embodiment 1, the difference is that the halogenation time is 2h, catalyst is denoted as C-07.Catalyst weight group becomes ZnBr₂It is 6.5%, P weight contents is 3% that weight content, which is 23.5%, ZnO weight contents,.Reaction condition is the same as embodiment 1.Catalyst 450 DEG C or less total acid contents are 0.81mmol/g in C-07, and 250 DEG C -350 DEG C of acid content accounts for 450 DEG C or less total acid contents 60.58%。

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.

Embodiment 8

With embodiment 1, the difference is that the halogenation time is 6h, catalyst is denoted as C-08.Catalyst weight group becomes ZnBr₂It is 2.8%, P weight contents is 3% that weight content, which is 33.9%, ZnO weight contents,.Reaction condition is the same as embodiment 1.Catalyst 450 DEG C or less total acid contents are 0.90mmol/g in C-08, and 250 DEG C -350 DEG C of acid content accounts for 450 DEG C or less total acid contents 62.04%。

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, reaction Pressure is 2MPa（Absolute pressure）, air speed 200h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa（Absolute pressure）, 800h^-1, recovery time 4h, after reduction Content of halogen in catalyst is restore total halogen content in procatalyst 37.84%.After stable reaction one hour, sampling point Analysis.Reaction result is shown in Table 1.

Embodiment 9

With embodiment 1, the difference is that halogenation temperature is 250 DEG C, catalyst is denoted as C-09.Catalyst weight group becomes ZnBr₂It is 5.6%, P weight contents is 3% that weight content, which is 26.1%, ZnO weight contents,.Reaction condition is the same as embodiment 1.Catalyst 450 DEG C or less total acid contents are 0.93mmol/g in C-09, and 250 DEG C -350 DEG C of acid content accounts for 450 DEG C or less total acid contents 64.11%.Reaction result is shown in Table 1.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, reaction Pressure is 2MPa（Absolute pressure）, air speed 200h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa（Absolute pressure）, 800h^-1, recovery time 4h, after reduction Content of halogen in catalyst is restore total halogen content in procatalyst 61.62%.After stable reaction one hour, sampling point Analysis.Reaction result is shown in Table 1.

Embodiment 10

With embodiment 1, the difference is that halogenation temperature is 300 DEG C, catalyst is denoted as C-10.Catalyst weight group becomes ZnBr₂It is 2.4%, P weight contents is 3% that weight content, which is 34.9%, ZnO weight contents,.Reaction condition is the same as embodiment 1.Catalyst 450 DEG C or less total acid contents are 1.05mmol/g in C-10, and 250 DEG C -350 DEG C of acid content accounts for 450 DEG C or less total acid contents 72.38%。

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, reaction Pressure is 2MPa（Absolute pressure）, air speed 200h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, mixing Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa（Absolute pressure）, 800h^-1, recovery time 4h, after reduction Content of halogen in catalyst is restore total halogen content in procatalyst 60.64%.After stable reaction one hour, sampling point Analysis.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, even if the difference is that progress activation zinc bromide Restore All completely is during preparing isobutene Zinc.Reaction result is shown in Table 1.

Table 1

Claims (26)

1. a kind of P Modification halide preparing isobutene catalyst, it is characterised in that：Based on the weight content of catalyst, zinc oxide Content is 0.5%-20%, and halogenation Zn content is 10%-50%, phosphorus content 0.1%-20%, vector contg 40%-85%, the halogen It includes one or more of zinc fluoride, zinc chloride, zinc bromide, zinc iodide to change zinc, and the carrier is aluminium oxide.

2. catalyst according to claim 1, it is characterised in that：Zinc oxide content is 1%-15%, and halogenation Zn content is 10%-45%, phosphorus content 0.1%-15%, vector contg 50%-85%, the zinc halide are zinc bromide.

3. catalyst according to claim 1, it is characterised in that：Zinc oxide content is 1%-9%, and halogenation Zn content is 18%- 39%, phosphorus content 0.5%-10%, vector contg 55%-80%.

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

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

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

7. the preparation method of one of the claim 1-6 catalyst, it is characterised in that：It comprises the following processes：（1）Using dipping P elements presoma is first carried on alumina support by method, and P Modification aluminium oxide is made after drying, roasting；It then proceedes to bear Zn-ef ficiency presoma is carried, catalyst precarsor can be made after drying, roasting；（2）To step（1）Gained catalyst precarsor carries out halogen Halide preparing isobutene catalyst can be made in change processing.

8. according to the method described in claim 7, it is characterized in that：Step（1）Described in Zn-ef ficiency presoma be zinc nitrate, chlorine Change one or more of zinc, zinc acetate.

9. according to the method described in claim 7, it is characterized in that：Step（1）Described in P elements presoma be phosphoric acid.

10. according to the method described in claim 7, it is characterized in that：Step（1）Middle carrying alumina shape be bar shaped, piece shape, Cylindricality or spherical shape.

11. according to the method described in claim 7, it is characterized in that：Step（1）Described in drying temperature be 50 DEG C -200 DEG C； Drying time is 1h-24h.

12. according to the method described in claim 7, it is characterized in that：Step（1）Described in calcination temperature be 200 DEG C -800 DEG C； Roasting time is 1h-24h.

13. according to the method described in claim 7, it is characterized in that：Step（2）Described in halogenation treatment using gas phase contain halogen Compound is to step（1）Gained sample is handled.

14. according to the method for claim 13, it is characterised in that：Halogen contained compound is a halide, dihalo first One or more of alkane, three halides.

15. according to the method for claim 13, it is characterised in that：Using the mixed of gas phase halogen contained compound and inert gas It closes gas and carries out halogenation treatment, gas phase halogen contained compound volumetric concentration is not less than 20%.

16. according to the method for claim 13, it is characterised in that：Halogenation process is as follows：By step（1）Sample be placed in company Afterflow is moved in fixed bed reactors, and 150 DEG C -400 DEG C are warming up under inert atmosphere, is passed through gas phase halogen contained compound gas, gas Body air speed is 50h^-1-1000 h^-1；It is carried out in normal pressure or under the conditions of pressure is 0.1MPa-0.5MPa when processing, when processing Between be 0.5h-8h.

17. according to the method for claim 16, it is characterised in that：180 DEG C -350 DEG C are warming up under inert atmosphere, gas space Speed is 100h^-1-500h^-1；System pressure is 0.1MPa-0.3MPa, processing time 1h-4h.

18. application of one of claim 1 to 6 catalyst in preparing isobutene, it is characterised in that：It is original with halide Material, reaction temperature are 150 DEG C -350 DEG C；Reaction pressure is 0.1MPa-5MPa；Air speed is 50h^-1-1000h^-1, needed before charging Reduction treatment is carried out to catalyst, it is the 20%- for restoring total halogen content in procatalyst to be restored to the content of halogen in catalyst 90%。

19. application according to claim 18, it is characterised in that：Reaction temperature is 180 DEG C -300 DEG C；Reaction pressure is 0.1MPa-3MPa；Air speed is 200h^-1-500h^-1, it is that halogen is total in reduction procatalyst to be restored to the content of halogen in catalyst The 30%-80% of content.

20. application according to claim 18, it is characterised in that：Reduction treatment process is as follows：It will catalysis under inert atmosphere Agent is warming up to 300 DEG C -600 DEG C；It is 200h to then pass to air speed^-1-2000h^-1Hydrogen or hydrogen and inert gas gaseous mixture Body 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%.

21. application according to claim 20, it is characterised in that：It is warming up to 350 DEG C -550 DEG C；Then passing to air speed is 500h^-1-1000h^-1Hydrogen or hydrogen and inert gas mixed gas, handle 4h-8h in 0.1MPa-0.3MPa, it is described mixed It is 30%-90% to close hydrogen volume percentage composition in gas.

22. application according to claim 18, 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.

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

24. application according to claim 18, it is characterised in that：Halide is a halide, methylene halide, three One or more of halide.

25. application according to claim 18, it is characterised in that：Halide is a bromomethane, methylene bromide, tribromo first One or more of alkane.

26. application according to claim 18, it is characterised in that：The reaction of halide preparing isobutene is in fixed bed, fluidisation It is carried out in bed, moving bed, slurry bed system or fluidized bed reactor.