CN106140232B - A kind of using titanium dioxide is carrier cerium as bromomethane preparing isobutene catalyst of auxiliary agent and the preparation method and application thereof - Google Patents

Abstract

It using titanium dioxide is carrier cerium as bromomethane preparing isobutene catalyst of auxiliary agent and the preparation method and application thereof that the present invention, which discloses a kind of,.The preparation method of the catalyst, includes the following steps：（1）Cerium oxide is introduced to titania support；（2）Zinc oxide is introduced to step（1）The titania support of gained；（3）Bromination processing, which is carried out, to being introduced into the catalyst precarsor after zinc oxide makes in catalyst zinc oxide weight content be 0.5% 5%, and preferably 1% 3%；Zinc bromide weight content is 5% 40%, preferably 10% 30%.The catalyst can significantly improve the selectivity of isobutene.

Description

It is a kind of using titanium dioxide be carrier cerium as the bromomethane preparing isobutene catalyst of auxiliary agent and Preparation method and application

Technical field

The present invention relates to a kind of preparation methods of bromomethane preparing isobutene catalyst, and it is to help to relate in particular to one kind with cerium Agent, titanium dioxide be carrier the highly selective preparing isobutene catalyst of bromomethane preparation method and applications.

Background technology

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

Methane is the main component of natural gas, therefore methane trans-utilization important grinding of just becoming in gas chemical industry's technology Study carefully content.Especially in recent years, under the overall background that shale gas develops and uses, if it is possible to realize from methane and produce isobutyl Alkene will provide a new approach to obtain isobutene.But methane property is stablized, and it is not easily-activated, become methane chemical industry profit Bottleneck.Domestic and international many researchers carry out methane activation, Study on Transformation one after another, and among these, methane is through halogen functional groupization The technology converted again afterwards is expected to become an important breakthrough mouth for solving methane transformation technology problem.

One many chemical products can be prepared from halide.Chinese patent CN 101041609A, CN 101284232A disclose it is a kind of by methane in oxygen and HBr/H₂Bromomethane is converted under the action of O, then bromomethane The hydrocarbon selective of the method that further reaction generates C3 ~ C13 mixing high-carbon hydrocarbons, C5 or more is 70%.Wherein, HBr is at first It is used for methane bromination in reactor, is then discharged in second reactor, is used further in back reaction, realizes after recovered The recycling of HBr.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 modified molecules of halide propylene Sieve catalyst and preparation method thereof.By using fluorochemical moditied processing molecular sieve, obtains one kind and containing appropriate microporous knot The catalyst of structure and acidity, the catalyst can effectively be catalyzed the reaction that halide is converted into propylene.Prepared catalysis Agent one way bromomethane conversion ratio in the preparing propylene transformed reaction of bromomethane is 35 ~ 99%, and the selectivity of propylene is 27 ~ 70%； One way methyl chloride conversion rate is 30 ~ 99% in the preparing propylene transformed reaction of chloromethanes, 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 bromo-hydrocarbons is generated with the alkane reaction in bromine and natural gas, Then bromo-hydrocarbons is converted to dimethyl ether, methanol and metal bromide, metal bromide oxygen on metal oxide catalyst Metal oxide is obtained after gas regeneration and releases simple substance bromine, completes the cycle of bromine.

Currently, being mainly methanol, dimethyl ether, acetic acid, high-carbon about purpose product in the existing literature of halide conversion Hydro carbons, ethylene and propylene etc..Using the low-carbon alkene compared with high added value as in the technology of target product, single selectivity of product It is not high, not yet find the relevant report of bromomethane high selectivity isobutene.

Invention content

In view of the deficiencies of the prior art, it is that carrier cerium is high as the bromomethane of auxiliary agent that the present invention provides a kind of using silica Selectively produce the preparation method and applications of isobutene catalyst.

A kind of preparation method of bromomethane preparing isobutene catalyst, includes the following steps：（1）Cerium oxide is introduced to dioxy Change titanium carrier；（2）Zinc oxide is introduced to step（1）The titania support of gained；（3）To the catalyst after introducing zinc oxide Precursor, which carries out bromination processing, makes zinc oxide weight content in catalyst be 0.5%-5%, preferably 1%-3%；Zinc bromide weight content is 5%-40%, preferably 10%-30%.

The preparation method step of above-mentioned bromomethane preparing isobutene catalyst（1）Described in cerium oxide be introduced to TiO 2 carrying The method of body is method well known to those skilled in the art, and impregnation method introducing such as may be used.The specific method is as follows：Using cerium Salt solution impregnated carrier, then dry, high-temperature roasting.The drying condition is, under air atmosphere, -150 DEG C of temperature 60 C is excellent It is selected as 80 DEG C -120 DEG C；Time is 1h-24h, preferably 4h-8h.The roasting condition is, under air atmosphere, 300 DEG C of temperature- 700 DEG C, preferably 400 DEG C -600 DEG C；Time is 1h-24h, preferably 4h-8h.Cerium salt described in the above method be cerous nitrate, The inorganic salts such as cerium chloride, cerous sulfate, preferably cerous nitrate.

In the preparation method of above-mentioned bromomethane preparing isobutene catalyst, existing dioxy may be used in the titania support Change titanium products, can also be prepared by method well known to those skilled in the art.Carrier can be made or select according to the needs used Suitable particle shape is taken, such as bar shaped, piece shape, cylindricality, spherical shape is made.Forming can be carried out by this field general knowledge.

The preparation method step of above-mentioned bromomethane preparing isobutene catalyst（2）Described in zinc oxide be introduced to TiO 2 carrying The method of body is method well known to those skilled in the art, and impregnation method introducing such as may be used.The specific method is as follows：Using zinc Salt solution impregnation step（1）Obtained material obtains bromomethane preparing isobutene catalyst precarsor after drying, roasting.It is described dry Dry condition is -150 DEG C of temperature 60 C, preferably 80 DEG C -120 DEG C；Time is 1h-24h, preferably 4h-8h；It can be with when dry For vacuum drying, or it is dry under the conditions of inert gas shielding, it can also dry in air atmosphere.The roasting condition For 300 DEG C -600 DEG C of temperature, preferably 400 DEG C -500 DEG C；Time is 1h-24h, preferably 4h-8h；Can be lazy when roasting It roasts, can also roast in air atmosphere under the conditions of property gas shield.

In the above method, zinc salt can be inorganic salts, or organic salt, preferably nitrate, hydrochloride, acetic acid One or more of salt, citrate.

The preparation method step of above-mentioned bromomethane preparing isobutene catalyst（3）Described in bromination processing, refer to use gas phase Bromine-containing compound handles the sample for loading zinc oxide.Bromine-containing compound refers in bromomethane, methylene bromide, bromoform One or more, preferably bromomethane.The mixed gas of gas phase bromine-containing compound and inert gas can also be used to carry out bromine Change is handled, and when being handled using mixed gas bromination, bromomethane volumetric concentration is not less than 20%, preferably not less than 30%.Specifically Bromination process is as follows：The sample for loading zinc oxide is placed in continuous fixed bed reactor, 150 are warming up under inert atmosphere DEG C -400 DEG C, preferably 180 DEG C -350 DEG C, more preferably 200 DEG C -300 DEG C, are passed through gas phase bromine-containing compound gas, gas space Speed is 50h^-1-1000 h^-1, preferably 100h^-1-500h^-1；Can be carried out in normal pressure when processing, can also under a certain pressure into Row, system pressure 0.1MPa-0.5MPa（Absolute pressure）, preferably 0.1MPa-0.3MPa（Absolute pressure）, processing time 0.5h-8h, It is preferred that 1h-4h.

Involved inert gas is nitrogen, argon gas, helium in the preparation method of above-mentioned bromomethane preparing isobutene catalyst Deng the gas not chemically reacted under the conditions of involved in the present invention, preferably nitrogen.

The bromomethane preparing isobutene catalyst, by zinc oxide, zinc bromide, auxiliary agent cerium oxide and titania support group At.Wherein, based on catalyst content, zinc oxide weight content is 0.5%-5%, preferably 1%-3%；Zinc bromide weight content is 5%- 40%, preferably 10%-30%；Cerium oxide weight content is 0.1%-2%, preferably 0.5%-1.5%；Titania support weight content 60%-95%, preferably 65%-90%.

In above-mentioned bromomethane preparing isobutene catalyst, 450 DEG C or less total acid contents（NH3-TPD）For 0.5mmol/g- 1.0mmol/g, preferably 0.7mmol/g-0.9mmol/g, 250 DEG C -350 DEG C of acid content account for the 20%- of 450 DEG C or less total acid contents 90%, preferably 30%-80%, further preferred 40%-80%.

The above-mentioned application using titanium dioxide containing cerium as the catalyst of carrier in preparing isobutene, including hydrogen is carried out to catalyst Gas reduction activation, it is the 20%-90% for restoring total halogen content in procatalyst to make the content of halogen in catalyst, is then made halogenated Catalyst after methane is activated with above-mentioned hydrogen reducing contacts, to prepare isobutene.

In above application, the condition of the hydrogen reducing activation so that the content of halogen in catalyst is preferably to be urged before restoring The 30%-80% of total halogen content in agent, further preferred 40%-80%.

In above application, the mode of hydrogen reducing activation include under an inert atmosphere by catalyzer temperature-elevating to 300 DEG C- 600℃；It is 200h to then pass to air speed^-1-2000h^-1Hydrogen or hydrogen and inert gas mixed gas, in 0.1MPa- 0.5MPa keeps 2h-16h, and hydrogen volume percentage composition is 10%-95% in mixed gas；Preferably, it is warming up to 350 DEG C -550 ℃；It is 500h to then pass to air speed^-1-1000h^-1Hydrogen or hydrogen and inert gas mixed gas, in 0.1MPa- 0.3MPa keeps 4h-8h, and hydrogen volume percentage composition is 30%-90% in the mixed gas.

The application of above-mentioned catalyst further includes that halide contacts acquisition isobutene with catalyst.The condition of the contact It it is 150 DEG C -350 DEG C including reaction temperature；Reaction pressure is 0.1MPa-5MPa；Air speed is 50h^-1-1000h^-1；It is highly preferred that Reaction temperature is 180 DEG C -300 DEG C more preferably 200-270 DEG C；Reaction pressure is 0.1MPa-3MPa；Air speed is 200h^-1- 500h^-1。

In above application, the halide can be one kind in a halide, methylene halide, three halides Or a variety of, preferably one or more in bromomethane, methylene bromide, bromoform, more preferably bromomethane.

A kind of specific implementation mode in above application, including 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 and inertia The mixed gas of gas, in 0.1MPa-0.5MPa（Absolute pressure）, preferably 0.1MPa-0.3MPa（Absolute pressure）2h-16h is handled, preferably After 4h-8h, it is down to reaction temperature and is passed through halide and reacted.Hydrogen volume percentage composition is 10%- in the gaseous mixture 95%, preferably 30%-90%, more preferably 50%-90%.

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

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

In above application, 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. In the present invention, cerium promoter has excellent electron transfer function, can constitute electron transmission between zinc and carrier titanium dioxide Bridge realizes electronics in ZnBr₂-ZnO-CeO₂-TiO₂Between transmission, improve TiO₂Effect between Zn promotes catalysis The removing of agent bromine in activation process improves selective isobutene.It is anti-that bromomethane conversion preparing isobutene is carried out by the method for the present invention It answers, 50% or more bromomethane conversion ratio, 60% or more selective isobutene.The present invention relates to bromomethanes to convert preparing isobutene catalyst Preparation method is simple, is easy to industrialize.With reaction condition, mild, product selects bromomethane conversion preparing isobutene method of the present invention The advantages that property is high, industrialization easy to implement, application prospect are boundless.

Specific implementation mode

The technology contents and effect further illustrated the present invention with reference to embodiment, but it is not so limited the present invention.

Acidimetric estimation uses NH in following embodiment and comparative example₃- TPD methods, the instrument model used is the U.S. 2920 chemical adsorption instruments of MICROMERITICS companies AutoChem, specific continuous mode are as follows：By sample at 450 DEG C with helium Purging is cooled to 150 DEG C after 1 hour, introduces the mixed gas of ammonia and helium, ammonia volume content 10%, and Pulse adsorption reaches for five times Balance；Then helium purge 2 hours carries out ammonia with 10 DEG C/min of heating rate temperature programming and is desorbed to 450 DEG C；After desorption Ammonia using TCD detectors detect, quantitatively calculate catalyst surface acid amount.

Embodiment 1

It weighs appropriate cerous nitrate to be dissolved in deionized water, titania support is carried on using equi-volume impregnating（Kong Rong For 0.37ml/g, specific surface area 103m²/ g, bar shaped, equivalent diameter 1.5mm）, 100 DEG C of dry 6h, 500 DEG C roast 6h, and system contains The titania support of cerium oxide.Appropriate zinc nitrate is weighed again to be dissolved in deionized water, is carried on and is contained using equi-volume impregnating Catalyst precarsor ZnO/CeO is made in the titania support of cerium oxide, 100 DEG C of dry 6h, 450 DEG C of roasting 6h₂/TiO₂.It will urge Agent precursor is placed in continuous fixed bed reactor, and catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, Bromomethane volumetric concentration is 60%, and treatment conditions are 250 DEG C, 0.2MPa（Absolute pressure）, 300h^-1, time 2h, be made bromomethane system it is different Butylene catalyst, is denoted as C-1.Obtaining catalyst weight group becomes ZnBr₂Weight content is 18%, ZnO to aoxidize in terms of bromide Object meter weight content is 2%, CeO₂Weight content is 1% in terms of oxide, and 450 DEG C or less total acid contents are in catalyst 0.83mmol/g, 250 DEG C -350 DEG C of acid content account for the 64.25% 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, Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 70% in mixed gas, activation condition It is 450 DEG C, 0.2MPa（Absolute pressure）, 750h^-1, soak time 6h；It is reduction procatalyst to restore the content of halogen in rear catalyst The 71.91% of middle total halogen content.

After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein Bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure 2MPa（Absolute pressure）, air speed 350h^-1.Stable reaction After one hour, sampling analysis.Reaction result is shown in Table 1.

Embodiment 2

It weighs appropriate cerous nitrate to be dissolved in deionized water, titania support is carried on using equi-volume impregnating（Kong Rong For 0.37ml/g, specific surface area 103m²/ g, bar shaped, equivalent diameter 1.5mm）, 120 DEG C of dry 4h, 400 DEG C roast 8h, and system contains The titania support of cerium oxide.Appropriate zinc nitrate is weighed again to be dissolved in deionized water, is carried on and is contained using equi-volume impregnating Catalyst precarsor ZnO/CeO is made in the titania support of cerium oxide, 100 DEG C of dry 6h, 400 DEG C of roasting 8h₂/TiO₂.It will urge Agent precursor is placed in continuous fixed bed reactor, and catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, Bromomethane volumetric concentration is 60%, and treatment conditions are 250 DEG C, 0.2MPa（Absolute pressure）, 300h^-1, time 2h, be made bromomethane system it is different Butylene catalyst, is denoted as C-2.Obtaining catalyst weight group becomes ZnBr₂Weight content is 18%, ZnO to aoxidize in terms of bromide Object meter weight content is 2%, CeO₂Weight content is 0.5% in terms of oxide, and 450 DEG C or less total acid contents are in catalyst 0.79mmol/g, 250 DEG C -350 DEG C of acid content account for the 57.25% 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, Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 70% in mixed gas, activation condition It is 450 DEG C, 0.2MPa（Absolute pressure）, 750h^-1, soak time 6h；It is reduction procatalyst to restore the content of halogen in rear catalyst The 78.37% of middle total halogen content.

After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein Bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure 2MPa（Absolute pressure）, air speed 350h^-1.Stable reaction After one hour, sampling analysis.Reaction result is shown in Table 1.

Embodiment 3

It weighs appropriate cerous nitrate to be dissolved in deionized water, titania support is carried on using equi-volume impregnating（Kong Rong For 0.37ml/g, specific surface area 103m²/ g, bar shaped, equivalent diameter 1.5mm）, 80 DEG C of dry 4h, 600 DEG C roast 4h, and system contains The titania support of cerium oxide.Appropriate zinc nitrate is weighed again to be dissolved in deionized water, is carried on and is contained using equi-volume impregnating Catalyst precarsor ZnO/CeO is made in the titania support of cerium oxide, 120 DEG C of dry 4h, 500 DEG C of roasting 4h₂/TiO₂.It will urge Agent precursor is placed in continuous fixed bed reactor, and catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, Bromomethane volumetric concentration is 60%, and treatment conditions are 250 DEG C, 0.2MPa（Absolute pressure）, 300h^-1, time 2h, be made bromomethane system it is different Butylene catalyst, is denoted as C-3.Obtaining catalyst weight group becomes ZnBr₂Weight content is 18%, ZnO to aoxidize in terms of bromide Object meter weight content is 2%, CeO₂Weight content is 1.5% in terms of oxide, and 450 DEG C or less total acid contents are in catalyst 0.85mmol/g, 250 DEG C -350 DEG C of acid content account for the 62.88% 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, Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 70% in mixed gas, activation condition It is 450 DEG C, 0.2MPa（Absolute pressure）, 750h^-1, soak time 6h；It is reduction procatalyst to restore the content of halogen in rear catalyst The 56.97% of middle total halogen content.

After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein Bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure 0.2MPa（Absolute pressure）, air speed 350h^-1.Reaction is steady After one hour fixed, sampling analysis.Reaction result is shown in Table 1.

Embodiment 4

It weighs appropriate cerous nitrate to be dissolved in deionized water, titania support is carried on using equi-volume impregnating（Kong Rong For 0.37ml/g, specific surface area 103m²/ g, bar shaped, equivalent diameter 1.5mm）, 100 DEG C of dry 6h, 500 DEG C roast 6h, and system contains The titania support of cerium oxide.Appropriate zinc nitrate is weighed again to be dissolved in deionized water, is carried on and is contained using equi-volume impregnating Catalyst precarsor ZnO/CeO is made in the titania support of cerium oxide, 100 DEG C of dry 6h, 450 DEG C of roasting 6h₂/TiO₂.It will urge Agent precursor is placed in continuous fixed bed reactor, and catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, Bromomethane volumetric concentration is 30%, and treatment conditions are 250 DEG C, 0.2MPa（Absolute pressure）, 300h^-1, time 2h, be made bromomethane system it is different Butylene catalyst, is denoted as C-4.Obtaining catalyst weight group becomes ZnBr₂Weight content is 15%, ZnO to aoxidize in terms of bromide Object meter weight content is 3%, CeO₂Weight content is 1% in terms of oxide, and 450 DEG C or less total acid contents are in catalyst 0.75mmol/g, 250 DEG C -350 DEG C of acid content account for the 63.97% 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, Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 50% in mixed gas, activation condition It is 550 DEG C, 0.1MPa（Absolute pressure）, 1000h^-1, soak time 4h；It is reduction procatalyst to restore the content of halogen in rear catalyst The 68.21% of middle total halogen content.

After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein Bromomethane volume content is 30%, and reaction temperature is 250 DEG C, reaction pressure 3MPa（Absolute pressure）, air speed 500h^-1.Stable reaction After one hour, sampling analysis.Reaction result is shown in Table 1.

Embodiment 5

It weighs appropriate cerous nitrate to be dissolved in deionized water, titania support is carried on using equi-volume impregnating（Kong Rong For 0.37ml/g, specific surface area 103m²/ g, bar shaped, equivalent diameter 1.5mm）, 100 DEG C of dry 6h, 500 DEG C roast 6h, and system contains The titania support of cerium oxide.Appropriate zinc nitrate is weighed again to be dissolved in deionized water, is carried on and is contained using equi-volume impregnating Catalyst precarsor ZnO/CeO is made in the titania support of cerium oxide, 100 DEG C of dry 6h, 450 DEG C of roasting 6h₂/TiO₂.It will urge Agent precursor is placed in continuous fixed bed reactor, and catalyst precarsor, treatment conditions 250 are handled using methyl bromide gas DEG C, 0.2MPa（Absolute pressure）, 300h^-1, time 2h is made bromomethane preparing isobutene catalyst, is denoted as C-5.Obtain catalyst weight Group becomes ZnBr₂It is 2%, CeO that weight content, which is 24%, ZnO weight contents in terms of oxide, in terms of bromide₂It is counted weight with oxide It is 1.5% to measure content, and 450 DEG C or less total acid contents are 0.88mmol/g in catalyst, 250 DEG C -350 DEG C of acid content account for 450 DEG C with The 54.29% of lower total acid content.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 90% in mixed gas, activation condition It is 350 DEG C, 0.3MPa（Absolute pressure）, 500h^-1, soak time 8h；It is reduction procatalyst to restore the content of halogen in rear catalyst The 58.56% of middle total halogen content.

After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein Bromomethane volume content is 80%, and reaction temperature is 210 DEG C, reaction pressure 0.1MPa（Absolute pressure）, air speed 200h^-1.Reaction is steady After one hour fixed, sampling analysis.Reaction result is shown in Table 1.

Embodiment 6

It weighs appropriate cerous nitrate to be dissolved in deionized water, titania support is carried on using equi-volume impregnating（Kong Rong For 0.37ml/g, specific surface area 103m²/ g, bar shaped, equivalent diameter 1.5mm）, 100 DEG C of dry 6h, 500 DEG C roast 6h, and system contains The titania support of cerium oxide.Appropriate zinc nitrate is weighed again to be dissolved in deionized water, is carried on and is contained using equi-volume impregnating Catalyst precarsor ZnO/CeO is made in the titania support of cerium oxide, 100 DEG C of dry 6h, 450 DEG C of roasting 6h₂/TiO₂.It will urge Agent precursor is placed in continuous fixed bed reactor, and catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, Bromomethane volumetric concentration is 60%, and treatment conditions are 250 DEG C, 0.2MPa（Absolute pressure）, 300h^-1, time 2h, be made bromomethane system it is different Butylene catalyst, is denoted as C-6.Obtaining catalyst weight group becomes ZnBr₂Weight content is 30%, ZnO to aoxidize in terms of bromide Object meter weight content is 1%, CeO₂Weight content is 0.5% in terms of oxide, and 450 DEG C or less total acid contents are in catalyst 0.89mmol/g, 250 DEG C -350 DEG C of acid content account for the 63.37% 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, Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 70% in mixed gas, activation condition It is 450 DEG C, 0.2MPa（Absolute pressure）, 750h^-1, soak time 6h；It is reduction procatalyst to restore the content of halogen in rear catalyst The 78.89% of middle total halogen content.

After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein Bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure 2MPa（Absolute pressure）, air speed 350h^-1.Stable reaction After one hour, sampling analysis.Reaction result is shown in Table 1.

Embodiment 7

It weighs appropriate cerous nitrate to be dissolved in deionized water, titania support is carried on using equi-volume impregnating（Kong Rong For 0.37ml/g, specific surface area 103m²/ g, bar shaped, equivalent diameter 1.5mm）, 100 DEG C of dry 6h, 500 DEG C roast 6h, and system contains The titania support of cerium oxide.Appropriate zinc nitrate is weighed again to be dissolved in deionized water, is carried on and is contained using equi-volume impregnating Catalyst precarsor ZnO/CeO is made in the titania support of cerium oxide, 100 DEG C of dry 6h, 450 DEG C of roasting 6h₂/TiO₂.It will urge Agent precursor is placed in continuous fixed bed reactor, and catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, Bromomethane volumetric concentration is 60%, and treatment conditions are 250 DEG C, 0.2MPa（Absolute pressure）, 300h^-1, time 2h, be made bromomethane system it is different Butylene catalyst, is denoted as C-7.Obtaining catalyst weight group becomes ZnBr₂Weight content is 10%, ZnO to aoxidize in terms of bromide Object meter weight content is 1%, CeO₂Weight content is 1% in terms of oxide, and 450 DEG C or less total acid contents are in catalyst 0.82mmol/g, 250 DEG C -350 DEG C of acid content account for the 62.94% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 70% in mixed gas, activation condition It is 450 DEG C, 0.2MPa（Absolute pressure）, 750h^-1, soak time 6h；It is reduction procatalyst to restore the content of halogen in rear catalyst The 69.21% of middle total halogen content.

After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein Bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure 2MPa（Absolute pressure）, air speed 350h^-1.Stable reaction After one hour, sampling analysis.Reaction result is shown in Table 1.

Embodiment 8

It weighs appropriate cerous nitrate to be dissolved in deionized water, titania support is carried on using equi-volume impregnating（Kong Rong For 0.37ml/g, specific surface area 103m²/ g, bar shaped, equivalent diameter 1.5mm）, 100 DEG C of dry 6h, 500 DEG C roast 6h, and system contains The titania support of cerium oxide.Appropriate zinc nitrate is weighed again to be dissolved in deionized water, is carried on and is contained using equi-volume impregnating Catalyst precarsor ZnO/CeO is made in the titania support of cerium oxide, 100 DEG C of dry 6h, 450 DEG C of roasting 6h₂/TiO₂.It will urge Agent precursor is placed in continuous fixed bed reactor, and catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, Bromomethane volumetric concentration is 60%, and treatment conditions are 200 DEG C, 0.3MPa（Absolute pressure）, 500h^-1, time 1h, be made bromomethane system it is different Butylene catalyst, is denoted as C-8.Obtaining catalyst weight group becomes ZnBr₂Weight content is 18%, ZnO to aoxidize in terms of bromide Object meter weight content is 2%, CeO₂Weight content is 1% in terms of oxide, and 450 DEG C or less total acid contents are in catalyst 0.81mmol/g, 250 DEG C -350 DEG C of acid content account for the 61.53% 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, Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 70% in mixed gas, activation condition It is 450 DEG C, 0.2MPa（Absolute pressure）, 750h^-1, soak time 6h；It is reduction procatalyst to restore the content of halogen in rear catalyst The 67.41% of middle total halogen content.

After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein Bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure 2MPa（Absolute pressure）, air speed 350h^-1.Stable reaction After one hour, sampling analysis.Reaction result is shown in Table 1.

Embodiment 9

It weighs appropriate cerous nitrate to be dissolved in deionized water, titania support is carried on using equi-volume impregnating（Kong Rong For 0.37ml/g, specific surface area 103m²/ g, bar shaped, equivalent diameter 1.5mm）, 100 DEG C of dry 6h, 500 DEG C roast 6h, and system contains The titania support of cerium oxide.Appropriate zinc nitrate is weighed again to be dissolved in deionized water, is carried on and is contained using equi-volume impregnating Catalyst precarsor ZnO/CeO is made in the titania support of cerium oxide, 100 DEG C of dry 6h, 450 DEG C of roasting 6h₂/TiO₂.It will urge Agent precursor is placed in continuous fixed bed reactor, and catalyst precarsor is handled using the mixed gas of bromomethane and nitrogen, Bromomethane volumetric concentration is 60%, and treatment conditions are 300 DEG C, 0.1MPa（Absolute pressure）, 100h^-1, time 4h, be made bromomethane system it is different Butylene catalyst, is denoted as C-9.Obtaining catalyst weight group becomes ZnBr₂Weight content is 18%, ZnO to aoxidize in terms of bromide Object meter weight content is 2%, CeO₂Weight content is 1% in terms of oxide, and 450 DEG C or less total acid contents are in catalyst 0.89mmol/g, 250 DEG C -350 DEG C of acid content account for the 58.29% 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, Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 70% in mixed gas, activation condition It is 450 DEG C, 0.2MPa（Absolute pressure）, 750h^-1, soak time 6h；It is reduction procatalyst to restore the content of halogen in rear catalyst The 68.91% of middle total halogen content.

After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein Bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure 2MPa（Absolute pressure）, air speed 350h^-1.Stable reaction After one hour, sampling analysis.Reaction result is shown in Table 1.

Comparative example 1

Catalyst is prepared by embodiment 1, does not use bromination to handle in preparation process.Detailed process is as follows：

It weighs appropriate cerous nitrate to be dissolved in deionized water, titania support is carried on using equi-volume impregnating（Kong Rong For 0.37ml/g, specific surface area 103m²/ g, bar shaped, equivalent diameter 1.5mm）, 100 DEG C of dry 6h, 500 DEG C roast 6h, and system contains The titania support of cerium oxide.Appropriate zinc nitrate is weighed again to be dissolved in deionized water, is carried on and is contained using equi-volume impregnating Catalyst D-1 is made in the titania support of cerium oxide, 100 DEG C of dry 6h, 450 DEG C of roasting 6h.Obtain catalyst weight composition For ZnO, weight content is 8%, CeO in terms of oxide₂Weight content is 1% in terms of oxide, 450 DEG C or less total acids in catalyst Amount is 0.26mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 34.17% 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, Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 70% in mixed gas, activation condition It is 450 DEG C, 0.2MPa（Absolute pressure）, 750h^-1, soak time 6h.

After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein Bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure 2MPa（Absolute pressure）, air speed 350h^-1.Stable reaction After one hour, sampling analysis.Reaction result is shown in Table 1.

Comparative example 2

It takes catalyst C-1 without reduction activation, directly carries out bromomethane conversion reaction.Unstripped gas is that bromomethane and nitrogen are mixed Gas is closed, wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure 2MPa（Absolute pressure）, air speed is 350h^-1.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.

Comparative example 3

It weighs appropriate cerous nitrate to be dissolved in deionized water, titania support is carried on using equi-volume impregnating（Kong Rong For 0.37ml/g, specific surface area 103m²/ g, bar shaped, equivalent diameter 1.5mm）, 100 DEG C of dry 6h, 500 DEG C roast 6h, and system contains The titania support of cerium oxide.Appropriate zinc bromide is weighed again to be dissolved in deionized water, is carried on and is contained using equi-volume impregnating Catalyst D-2 is made in the titania support of cerium oxide, 100 DEG C of dry 6h, the lower 450 DEG C of roastings 6h of nitrogen atmosphere.It is catalyzed Agent weight group becomes ZnBr₂Weight content is 18%, CeO in terms of bromide₂Weight content is 1% in terms of oxide, in catalyst 450 DEG C or less total acid contents are 1.01mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 37.94% of 450 DEG C or less total acid contents.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Catalyst is activated using preceding using the gaseous mixture of hydrogen and nitrogen, and hydrogen volume content is 70% in mixed gas, activation condition It is 450 DEG C, 0.2MPa（Absolute pressure）, 750h^-1, soak time 6h；It is reduction procatalyst to restore the content of halogen in rear catalyst The 85.20% of middle total halogen content.

After activation, it to be down to reaction temperature, is passed through unstripped gas, unstripped gas is bromomethane and nitrogen mixed gas, wherein Bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure 2MPa（Absolute pressure）, air speed 350h^-1.Stable reaction After one hour, sampling analysis.Reaction result is shown in Table 1.

1 catalyst reaction performance of table

Claims (25)

1. a kind of preparation method of bromomethane preparing isobutene catalyst, it is characterised in that：Include the following steps：（1）By cerium oxide Being introduced to titania support makes cerium oxide weight content in catalyst be 0.1%-2%；（2）Zinc oxide is introduced to step（1） The titania support of gained；（3）Bromination processing, which is carried out, to being introduced into the catalyst precarsor after zinc oxide makes zinc oxide in catalyst Weight content is 0.5%-5%；Zinc bromide weight content is 5%-40%.

2. according to the method described in claim 1, it is characterized in that：Step（1）Described in cerium oxide be introduced to TiO 2 carrying Body uses impregnation method.

3. according to the method described in claim 2, it is characterized in that：Using cerium solution impregnated carrier, then dry, roasting, The drying condition is 60 DEG C -150 DEG C of drying temperature, drying time 1h-24h；The roasting condition is calcination temperature 300 DEG C -700 DEG C, roasting time 1h-24h.

4. according to the method described in claim 3, it is characterized in that：The cerium salt is cerous nitrate, cerium chloride or cerous sulfate.

5. according to the method described in claim 1, it is characterized in that：Step（2）Described in zinc oxide be introduced to TiO 2 carrying Body uses impregnation method.

6. according to the method described in claim 5, it is characterized in that：Using zinc solution impregnation steps（1）Obtained material, warp Bromomethane preparing isobutene catalyst precarsor is obtained after dry, roasting, the drying condition is -150 DEG C of temperature 60 C, and the time is 1h-24h, the roasting condition are 300 DEG C -600 DEG C of temperature, time 1h-24h.

7. according to the method described in claim 5, it is characterized in that：Zinc salt is nitrate, hydrochloride, acetate, citrate One or more of.

8. according to the method described in claim 1, it is characterized in that：Step（3）Described in bromination processing, refer to being contained using gas phase Bromine compounds handles the sample for loading zinc oxide.

9. according to the method described in claim 8, it is characterized in that：Bromine-containing compound refers to bromomethane, methylene bromide, tribromo first One or more of alkane.

10. according to the method described in claim 1, it is characterized in that：Step（3）It is middle to use gas phase bromine-containing compound and indifferent gas The mixed gas of body carries out bromination processing, and bromomethane volumetric concentration is not less than 20%.

11. according to the method described in claim 1, it is characterized in that：Step（3）In specific bromination process it is as follows：Oxygen will be loaded The sample for changing zinc is placed in continuous fixed bed reactor, and 150 DEG C -400 DEG C are warming up under inert atmosphere, it is brominated to be passed through gas phase Chemical compound gas, gas space velocity 50h^-1-1000 h^-1；System pressure is 0.1MPa-0.5MPa, processing time 0.5h-8h.

12. according to the method for claim 11, it is characterised in that：It is warming up to 180 DEG C -350 DEG C under inert atmosphere, is passed through gas Phase bromine-containing compound gas, gas space velocity 100h^-1-500h^-1；System pressure is 0.1MPa-0.3MPa, processing time 1h- 4h。

13. catalyst prepared by claim 1 to 12 either method, it is characterised in that：Catalyst by zinc oxide, zinc bromide, help Agent cerium oxide and titania support composition, zinc oxide weight content are 0.5%-5%；Zinc bromide weight content is 5%-40%；Oxygen Change cerium weight content is 0.1%-2%.

14. catalyst according to claim 13, it is characterised in that：Zinc oxide weight content is 1%-5%；Zinc bromide weight Content is 5%-30%；Cerium oxide weight content is 0.5%-1.5%.

15. catalyst according to claim 13, it is characterised in that：In catalyst, with NH₃- TPD counts 450 DEG C or less always Acid amount is 0.5mmol/g-1.0mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 20%-90% of 450 DEG C or less total acid contents.

16. application of any catalyst of claim 13-15 in preparing isobutene, it is characterised in that：Including being carried out to catalyst Hydrogen reducing activates, and it is the 20%-90% for restoring total halogen content in procatalyst to make the content of halogen in catalyst, then makes halogen Catalyst after being activated with above-mentioned hydrogen reducing for methane contacts, to prepare isobutene.

17. application according to claim 16, it is characterised in that：The condition of the hydrogen reducing activation makes in catalyst Content of halogen be restore procatalyst in total halogen content 30%-80%.

18. application according to claim 16, it is characterised in that：The mode of the hydrogen reducing activation is included in indifferent gas By catalyzer temperature-elevating to 300 DEG C -600 DEG C under atmosphere；It is 200h to then pass to air speed^-1-2000h^-1Hydrogen or hydrogen and indifferent gas The mixed gas of body, hydrogen volume percentage composition is 10%-95% in 0.1MPa-0.5MPa holding 2h-16h, mixed gas.

19. application according to claim 18, 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, keep 4h-8h in 0.1MPa-0.3MPa, it is described mixed It is 30%-90% to close hydrogen volume percentage composition in gas.

20. application according to claim 16, it is characterised in that：The condition of the contact include reaction temperature be 150 DEG C- 350℃；Reaction pressure is 0.1MPa-5MPa；Air speed is 50h^-1-1000h^-1。

21. application according to claim 20, 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。

22. application according to claim 16, it is characterised in that：The halide is a halide, dihalo first It is one or more in alkane, three halides.

23. application according to claim 16, it is characterised in that：The halide is bromomethane, methylene bromide, tribromo It is one or more in methane.

24. application according to claim 16, it is characterised in that：Including under inert atmosphere by catalyzer temperature-elevating to 300 DEG C- 600℃；It is 200h to then pass to air speed^-1-2000h^-1Hydrogen and inert gas mixed gas, at 0.1MPa-0.5MPa After managing 2h-16h, it is down to reaction temperature and is passed through halide and reacted, hydrogen volume percentage composition is in the gaseous mixture 10%-95%。

25. application according to claim 24, it is characterised in that：Including under inert atmosphere by catalyzer temperature-elevating to 350 DEG C- 550℃；It is 500h to then pass to air speed^-1-1000h^-1Hydrogen and inert gas mixed gas, at 0.1MPa-0.3MPa It after managing 4h-8h, is down to reaction temperature and is passed through halide and reacted, hydrogen volume percentage composition is 30%- in the gaseous mixture 90%。