CN106140264B - It is a kind of using lanthanum modified zsm-5 zeolite as catalyst of carrier and its preparation method and application - Google Patents

Abstract

The present invention discloses a kind of using lanthanum modified zsm-5 zeolite as catalyst of carrier and its preparation method and application.The preparation method of the catalyst, comprises the following processes: (1) using lanthanum salt solution impregnation Hydrogen ZSM-5 molecular sieve, obtain the modified Hydrogen ZSM-5 molecular sieve carrier of lanthanum；(2) zinc oxide is introduced to the modified Hydrogen ZSM-5 molecular sieve carrier of lanthanum；(3) bromination processing is carried out to the lanthanum modified zsm-5 zeolite carrier after introducing zinc oxide.The catalyst of this method preparation can be used for the reaction of bromomethane preparing isobutene, have many advantages, such as that bromomethane high conversion rate, selective isobutene are high.

Description

It is a kind of using lanthanum modified zsm-5 zeolite as catalyst of carrier and preparation method thereof and Using

Technical field

The present invention relates to a kind of using lanthanum modified zsm-5 zeolite as catalyst of carrier 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, under the overall background of shale gas development and utilization, 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 benefit 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.

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 further method that reaction generates C3 ~ C13 mixing high-carbon hydrocarbon, the hydrocarbon selective of C5 or more are 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.(CN 102527427A, Jieli He, Ting Xu, the Zhihui Wang, et.al. such as Wang Ye 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 contain 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 dimethyl ether, methanol and metal bromide, metal bromide oxygen are converted by bromo-hydrocarbons on metal oxide catalyst Metal oxide is obtained after gas regeneration and releases simple substance bromine, completes the circulation 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..In the technology using the low-carbon alkene compared with high added value as target product, single selectivity of product It is not high, not yet find the relevant report of bromomethane high selectivity isobutene.

Summary of the invention

In view of the deficiencies of the prior art, the present invention provide it is a kind of using lanthanum modified zsm-5 zeolite as the catalyst of carrier and Preparation method and application.

It is a kind of using lanthanum modified zsm-5 zeolite as the preparation method of the catalyst of carrier, comprise the following processes: (1) using lanthanum Salt solution impregnation handles Hydrogen ZSM-5 molecular sieve, obtains the modified Hydrogen ZSM-5 molecular sieve carrier of lanthanum；(2) zinc oxide is introduced To the modified Hydrogen ZSM-5 molecular sieve carrier of lanthanum；(3) the lanthanum modified zsm-5 zeolite carrier after introducing zinc oxide is carried out Incomplete bromination processing, even if so-called incomplete bromination processing zinc oxide portion is converted into zinc bromide.

In above-mentioned preparation method step (1), the Hydrogen ZSM-5 molecular sieve carrier can be existing commercial product, It can be prepared by those skilled in the art's well-known process.Carrier can be made or choose according to the needs of use suitable granulated State, such as bar shaped, piece shape, cylindricality, spherical shape is made, forming can be carried out by this field general knowledge.

It is isometric using the aqueous solution containing lanthanum salt and water soluble polymer in above-mentioned preparation method step (1) Hydrogen ZSM-5 molecular sieve carrier is impregnated, 4h-12h, preferably 4h-8h, 80 DEG C -120 DEG C dry 6h-12h, then at air gas are stood Under atmosphere, 500 DEG C of -700 DEG C of roasting 4h-8h Hydrogen ZSM-5 molecular sieves modified to get lanthanum are risen to 1 DEG C/min ~ 3 DEG C/min.Institute Stating lanthanum salt is the inorganic salts, preferably lanthanum nitrate such as lanthanum nitrate, lanthanum chloride, lanthanum sulfate；What the water soluble polymer referred to It is one or more of polyacrylamide (PAM) or polyvinylpyrrolidone (PVP), preferably polyvinylpyrrolidone, and The mass ratio of water soluble polymer and lanthanum is 2 ~ 5.

In above-mentioned preparation method step (2), method that the zinc oxide is introduced to lanthanum modified hydrogen ZSM-5 molecular sieve carrier For method well known to those skilled in the art, can such as be introduced using impregnation method.The specific method is as follows: being soaked using zinc solution The modified carrier of stain obtains bromomethane preparing isobutene catalyst precarsor after drying, roasting.The drying condition is temperature 60 DEG C -150 DEG C, preferably 80 DEG C -120 DEG C；Time is 1h-24h, preferably 4h-8h；It can be vacuum drying when dry, It can be drying under the conditions of inert gas shielding, can also dry in air atmosphere.The roasting condition is 300 DEG C of temperature- 800 DEG C, preferably 400 DEG C -600 DEG C；Time is 1h-24h, preferably 4h-8h；It can be inert gas shielding condition when roasting Lower roasting, can also roast in air atmosphere.In the above method, zinc salt can be inorganic salts, or organic salt, preferably For one or more of nitrate, hydrochloride, acetate, citrate.

In above-mentioned preparation method step (3), the bromination processing refers to using gas phase bromine-containing compound to load zinc oxide Sample handled.Bromine-containing compound refers to one or more of bromomethane, methylene bromide, bromoform, preferably bromine Methane.Bromination processing can also be carried out using the mixed gas of gas phase bromine-containing compound and inert gas, using mixed gas bromine When changing processing, bromomethane volumetric concentration is not less than 20%, preferably not less than 30%.Specific bromination process is as follows: will load oxygen The sample for changing zinc is placed in continuous fixed bed reactor, is warming up to 150 DEG C -400 DEG C under inert atmosphere, preferably 180 DEG C - 350 DEG C, more preferably 200 DEG C -300 DEG C are passed through gas phase bromine-containing compound gas, gas space velocity 50h^-1-1000 h^-1, preferably For 100h^-1-500h^-1；It can carry out, can also carry out under a certain pressure, system pressure 0.1MPa- in normal pressure when processing 0.5MPa(absolute pressure), preferably 0.1MPa-0.3MPa(absolute pressure), the processing time is 0.5h-8h, preferably 1h-4h.

In above-mentioned preparation method step (3), related inert gas is nitrogen, argon gas, helium etc. involved by the present invention The gas not chemically reacted under the conditions of and, preferably nitrogen.

It is a kind of using lanthanum modified zsm-5 zeolite as the catalyst of carrier, the catalyst is changed by zinc oxide, zinc bromide and lanthanum Property Hydrogen ZSM-5 molecular sieve carrier composition, based on the weight content of catalyst, zinc oxide content 0.5%-20%, preferably 1%-15%, further preferably 1%-9%, bromination Zn content are 10%-50%, preferably 15%-45%, further preferably 18%- 39%, the modified Hydrogen ZSM-5 molecular sieve vector contg of lanthanum is 40%-90%, preferably 50%-85%, further preferably 55%- 80%, in the modified Hydrogen ZSM-5 molecular sieve carrier of the lanthanum, weight content of the lanthanum in terms of lanthana in the carrier is 1%-5%, Hydrogen ZSM-5 molecular sieve carrier silica alumina ratio is 20 ~ 200, preferably 20 ~ 150.

In catalyst of the present invention, 450 DEG C or less total acid content (NH₃- TPD) it is 0.5mmol/g-1.3mmol/g, preferably 0.6mmol/g-1.2mmol/g, further preferred 0.7mmol-1.1mmol/g, 250 DEG C -350 DEG C of acid content account for 450 DEG C with The 20%-90% of lower total acid content, preferably 30%-80%, further preferred 40%-80%.

The above-mentioned application using modified zsm-5 zeolite as the catalyst of carrier in preparing isobutene, including to catalyst into The activation of row hydrogen reducing makes the content of halogen in catalyst restore the 20%-90% of total halogen content in procatalyst, then makes Catalyst after halide is activated with above-mentioned hydrogen reducing contacts, to prepare isobutene.

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

In above-mentioned application, the mode of hydrogen reducing activation include under an inert atmosphere by catalyzer temperature-elevating to 300 DEG C- 600℃；Then passing to air speed is 200h^-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 ℃；Then passing to air speed is 500h^-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.

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

In above-mentioned application, the condition of the contact includes that reaction temperature is 150 DEG C -350 DEG C；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。

By catalyzer temperature-elevating to 300 DEG C -600 DEG C under one of above-mentioned application specific embodiment, including inert atmosphere, Preferably 350 DEG C -550 DEG C；Then passing to air speed is 200h^-1-2000h^-1, preferably 500h^-1-1000h^-1Hydrogen or hydrogen With the mixed gas of inert gas, in 0.1MPa-0.5MPa(absolute pressure), preferably 0.1MPa-0.3MPa(absolute pressure) processing 2h- After 16h, preferably 4h-8h, it is down to reaction temperature and is passed through halide and reacted.Hydrogen volume percentage contains in the gaseous mixture Amount 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, 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, catalyst prepared by the present invention can by bromomethane it is highly selective be converted into isobutene. In the present invention, lanthanum is both the modifying agent of carrier and effective auxiliary agent of bromomethane conversion preparing isobutene catalyst, in addition, water The addition of soluble macromolecular polymer can also promote lanthana preferably to disperse on carrier.Bromomethane is carried out by the method for the present invention Convert preparing isobutene reaction, 85% or more bromomethane conversion ratio, 50% or more selective isobutene.The present invention relates to bromomethane conversions Preparing isobutene method for preparing catalyst is simple, is easy to industrialize.Bromomethane conversion preparing isobutene method of the present invention has reaction item The advantages that part is mild, selectivity of product is high, 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 are not so limited the present invention.

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

Embodiment 1

Weigh appropriate lanthanum nitrate and PVP(K30) it is dissolved in deionized water, Hydrogen ZSM- is carried on using equi-volume impregnating 5 molecular sieve carriers (silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m²/ g, bar shaped, equivalent diameter 1.5mm), it is quiet 6h, 100 DEG C of dry 9h are set, 600 DEG C of roasting 6h are risen to the heating rate of 1 DEG C/min, the modified Hydrogen ZSM-5 molecule of lanthanum is made Carrier is sieved, for lanthanum in terms of lanthana, weight content in the carrier is 3%.

It weighs appropriate zinc nitrate to be dissolved in deionized water, the modified Hydrogen of above-mentioned lanthanum is carried on using equi-volume impregnating Catalyst precarsor ZnO/La-ZSM-5 is made in ZSM-5 molecular sieve carrier, 80 DEG C of dry 8h, 600 DEG C of roasting 4h.By 5g catalyst Precursor is placed in continuous fixed bed reactor, handles catalyst precarsor using bromomethane, and treatment conditions are 250 DEG C, 0.2MPa(absolute pressure), 100h^-1, time 2h, be made bromomethane preparing isobutene catalyst, be denoted as C-1.Catalyst weight group becomes ZnBr₂Weight content is that 27%, ZnO weight content is 6%, and 450 DEG C or less total acid contents are 0.77mmol/g in catalyst, 250 DEG C- 350 DEG C of acid content accounts for the 52.1% 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 bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 50%, and reaction temperature is 230 DEG C, reaction pressure For 1MPa(absolute pressure), air speed 500h^-1, it being passed through unstripped gas procatalyst and activates in a hydrogen atmosphere, reducing condition is 400 DEG C, 0.2MPa(absolute pressure), 1000h^-1, recovery time 4h, restoring the content of halogen in rear catalyst is that halogen is total in reduction procatalyst The 61.38% of content.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.

Embodiment 2

Weigh appropriate lanthanum nitrate and PVP(K30) it is dissolved in deionized water, Hydrogen ZSM- is carried on using equi-volume impregnating 5 molecular sieve carriers (silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m²/ g, bar shaped, equivalent diameter 1.5mm), it is quiet 6h, 100 DEG C of dry 9h are set, 600 DEG C of roasting 6h are risen to the heating rate of 1 DEG C/min, the modified Hydrogen ZSM-5 molecule of lanthanum is made Carrier is sieved, for lanthanum in terms of lanthana, weight content in the carrier is 3%.

It weighs appropriate zinc nitrate to be dissolved in deionized water, the modified Hydrogen of above-mentioned lanthanum is carried on using equi-volume impregnating Catalyst precarsor ZnO/La-ZSM-5 is made in ZSM-5 molecular sieve carrier, 120 DEG C of dry 4h, 500 DEG C of roasting 8h.By 5g catalyst Precursor is placed in continuous fixed bed reactor, handles catalyst precarsor, bromine first using the mixed gas of bromomethane and nitrogen Alkane volumetric concentration is 80%, and treatment conditions are 250 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 2h, obtained bromomethane preparing isobutene Catalyst is denoted as C-2.Catalyst weight group is obtained as ZnBr₂Weight content is 30%, ZnO in terms of oxide in terms of bromide Weight content is 4%, and 450 DEG C or less total acid contents are 0.8mmol/g in catalyst, 250 DEG C -350 DEG C of acid content account for 450 DEG C with The 56.2% of lower total acid content.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure For 2MPa(absolute pressure), air speed 200h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, 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 47.96%.After stable reaction one hour, sampling point Analysis.Reaction result is shown in Table 1.

Embodiment 3

Weigh appropriate lanthanum nitrate and PVP(K30) it is dissolved in deionized water, Hydrogen ZSM- is carried on using equi-volume impregnating 5 molecular sieve carriers (silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m²/ g, bar shaped, equivalent diameter 1.5mm), it is quiet 6h, 100 DEG C of dry 9h are set, 600 DEG C of roasting 6h are risen to the heating rate of 1 DEG C/min, the modified Hydrogen ZSM-5 molecule of lanthanum is made Carrier is sieved, for lanthanum in terms of lanthana, weight content in the carrier is 3%.

It weighs appropriate zinc nitrate to be dissolved in deionized water, the modified Hydrogen of above-mentioned lanthanum is carried on using equi-volume impregnating Catalyst precarsor ZnO/La-ZSM-5 is made in ZSM-5 molecular sieve carrier, 100 DEG C of vacuum drying 8h, 400 DEG C of roasting 8h.5g is urged Agent precursor is placed in continuous fixed bed reactor, handles catalyst precarsor using the mixed gas of bromomethane and nitrogen, Bromomethane volumetric concentration is 30%, and treatment conditions are 300 DEG C, 0.1MPa(absolute pressure), 500h^-1, time 4h, be made bromomethane system it is different Butylene catalyst, is denoted as C-3.Catalyst weight group is obtained as ZnBr₂Weight content is 33%, ZnO to aoxidize in terms of bromide Object meter weight content is 2%, and 450 DEG C or less total acid contents are 0.82mmol/g in catalyst, and 250 DEG C -350 DEG C of acid content accounts for 450 DEG C or less total acid content 59.7%.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 80%, and reaction temperature is 200 DEG C, reaction pressure For 3MPa(absolute pressure), air speed 350h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, 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 43.23%.After stable reaction one hour, sampling point Analysis.Reaction result is shown in Table 1.

Embodiment 4

Weigh appropriate lanthanum nitrate and PVP(K30) it is dissolved in deionized water, Hydrogen ZSM- is carried on using equi-volume impregnating 5 molecular sieve carriers (silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m²/ g, bar shaped, equivalent diameter 1.5mm), it is quiet 6h, 100 DEG C of dry 9h are set, 600 DEG C of roasting 6h are risen to the heating rate of 1 DEG C/min, the modified Hydrogen ZSM-5 molecule of lanthanum is made Carrier is sieved, for lanthanum in terms of lanthana, weight content in the carrier is 3%.

It weighs appropriate zinc nitrate to be dissolved in deionized water, the modified Hydrogen of above-mentioned lanthanum is carried on using equi-volume impregnating Catalyst precarsor ZnO/La-ZSM-5 is made in ZSM-5 molecular sieve carrier, 120 DEG C of dry 4h, 500 DEG C of roasting 8h.By 5g catalyst Precursor is placed in continuous fixed bed reactor, handles catalyst precarsor using bromomethane, and treatment conditions are 200 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 1h, be made bromomethane preparing isobutene catalyst, be denoted as C-4.Obtain catalyst weight composition For ZnBr₂It is 2% that weight content, which is 18%, ZnO weight content in terms of oxide, in terms of bromide, in catalyst 450 DEG C or less it is total Acid amount is 0.73mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 49.8% 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 bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 30%, and reaction temperature is 270 DEG C, reaction pressure For 2MPa(absolute pressure), air speed 350h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, 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 52.39%.After stable reaction one hour, sampling point Analysis.Reaction result is shown in Table 1.

Embodiment 5

Weigh appropriate lanthanum nitrate and PVP(K30) it is dissolved in deionized water, Hydrogen ZSM- is carried on using equi-volume impregnating 5 molecular sieve carriers (silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m²/ g, bar shaped, equivalent diameter 1.5mm), it is quiet 6h, 100 DEG C of dry 9h are set, 600 DEG C of roasting 6h are risen to the heating rate of 1 DEG C/min, the modified Hydrogen ZSM-5 molecule of lanthanum is made Carrier is sieved, for lanthanum in terms of lanthana, weight content in the carrier is 5%.

It weighs appropriate zinc nitrate to be dissolved in deionized water, the modified Hydrogen of above-mentioned lanthanum is carried on using equi-volume impregnating ZSM-5 molecular sieve carrier, 100 DEG C of dry 6h roast 6h under 500 DEG C of nitrogen protections, and catalyst precarsor ZnO/La-ZSM-5 is made. 5g catalyst precarsor is placed in continuous fixed bed reactor, handles catalyst using the mixed gas of bromomethane and nitrogen Precursor, bromomethane volumetric concentration are 70%, and treatment conditions are 200 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 2h, obtained bromomethane Preparing isobutene catalyst, is denoted as C-5.Catalyst weight group is obtained as ZnBr₂In terms of bromide weight content be 39%, ZnO with Oxide meter weight content is 6%, and 450 DEG C or less total acid contents are 0.86mmol/g, 250 DEG C -350 DEG C of acid content in catalyst Account for the 64.1% 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 bromomethane, and reaction temperature is 270 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed 350h^-1.Before being passed through unstripped gas, Catalyst activates under the mixed atmosphere of hydrogen and nitrogen, 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 43.51% of total content.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.

Embodiment 6

Weigh appropriate lanthanum nitrate and PVP(K30) it is dissolved in deionized water, Hydrogen ZSM- is carried on using equi-volume impregnating 5 molecular sieve carriers (silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m²/ g, bar shaped, equivalent diameter 1.5mm), it is quiet 6h, 100 DEG C of dry 9h are set, 600 DEG C of roasting 6h are risen to the heating rate of 1 DEG C/min, the modified Hydrogen ZSM-5 molecule of lanthanum is made Carrier is sieved, for lanthanum in terms of lanthana, weight content in the carrier is 3%.

It weighs appropriate zinc nitrate to be dissolved in deionized water, the modified Hydrogen of above-mentioned lanthanum is carried on using equi-volume impregnating ZSM-5 molecular sieve carrier, dry 4h under 120 DEG C of nitrogen atmospheres roast 4h under 500 DEG C of nitrogen atmospheres, catalyst precarsor are made ZnO/La-ZSM-5.5g catalyst precarsor is placed in continuous fixed bed reactor, before handling catalyst using bromomethane Body, treatment conditions are 250 DEG C, 0.2MPa(absolute pressure), 100h^-1, time 1h is denoted as C-6.Obtaining catalyst weight group becomes ZnBr₂It is 9% that weight content, which is 35%, ZnO weight content in terms of oxide, in terms of bromide, 450 DEG C or less total acids in catalyst Amount is 0.84mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 61.9% 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 bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 50%, and reaction temperature is 230 DEG C, reaction pressure For 0.1MPa(absolute pressure), air speed 500h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, 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 50.93%.After stable reaction one hour, sampling Analysis.Reaction result is shown in Table 1.

Embodiment 7

Weigh appropriate lanthanum nitrate and PVP(K30) it is dissolved in deionized water, Hydrogen ZSM- is carried on using equi-volume impregnating 5 molecular sieve carriers (silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m²/ g, bar shaped, equivalent diameter 1.5mm), it is quiet 6h, 100 DEG C of dry 9h are set, 600 DEG C of roasting 6h are risen to the heating rate of 1 DEG C/min, the modified Hydrogen ZSM-5 molecule of lanthanum is made Carrier is sieved, for lanthanum in terms of lanthana, weight content in the carrier is 1%.

It weighs appropriate zinc nitrate to be dissolved in deionized water, the modified Hydrogen of above-mentioned lanthanum is carried on using equi-volume impregnating Catalyst precarsor ZnO/La-ZSM-5 is made in ZSM-5 molecular sieve carrier, 120 DEG C of dry 4h, 500 DEG C of roasting 4h.By 5g catalyst Precursor is placed in continuous fixed bed reactor, handles catalyst precarsor, bromine first using the mixed gas of bromomethane and nitrogen Alkane volumetric concentration is 90%, and treatment conditions are 300 DEG C, 0.1MPa(absolute pressure), 500h^-1, time 4h, obtained bromomethane preparing isobutene Catalyst is denoted as C-7.Catalyst weight group is obtained as ZnBr₂Weight content is 20%, ZnO in terms of oxide in terms of bromide Weight content is 1%, and 450 DEG C or less total acid contents are 0.74mmol/g in catalyst, 250 DEG C -350 DEG C of acid content account for 450 DEG C with The 51.2% of lower total acid content.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 80%, and reaction temperature is 200 DEG C, reaction pressure For 3MPa(absolute pressure), air speed 350h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, 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 54.48%.After stable reaction one hour, sampling point Analysis.Reaction result is shown in Table 1.

Comparative example 1

Weigh appropriate lanthanum nitrate and PVP(K30) it is dissolved in deionized water, Hydrogen ZSM- is carried on using equi-volume impregnating 5 molecular sieve carriers (silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m²/ g, bar shaped, equivalent diameter 1.5mm), it is quiet 6h, 100 DEG C of dry 9h are set, 600 DEG C of roasting 6h are risen to the heating rate of 1 DEG C/min, the modified Hydrogen ZSM-5 molecule of lanthanum is made Carrier is sieved, for lanthanum in terms of lanthana, weight content in the carrier is 3%.

It weighs appropriate zinc nitrate to be dissolved in deionized water, the modified Hydrogen of above-mentioned lanthanum is carried on using equi-volume impregnating ZSM-5 molecular sieve carrier, 120 DEG C of dry 4h, 500 DEG C of roasting 4h are made catalyst Z nO/La-ZSM-5, are denoted as D-1.It is urged It is 20% that agent weight group, which becomes ZnO weight content in terms of oxide, and 450 DEG C or less total acid contents are 0.41mmol/g in catalyst, 250 DEG C -350 DEG C of acid content accounts for the 39.5% 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 bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure For 2MPa(absolute pressure), air speed 200h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, mixing Hydrogen volume content is 80% in gas, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h^-1, recovery time 4h.Reaction is steady After one hour fixed, sampling analysis.Reaction result is shown in Table 1.

Comparative example 2

Weigh appropriate lanthanum nitrate and PVP(K30) it is dissolved in deionized water, Hydrogen ZSM- is carried on using equi-volume impregnating 5 molecular sieve carriers (silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m²/ g, bar shaped, equivalent diameter 1.5mm), it is quiet 6h, 100 DEG C of dry 9h are set, 600 DEG C of roasting 6h are risen to the heating rate of 1 DEG C/min, the modified Hydrogen ZSM-5 molecule of lanthanum is made Carrier is sieved, for lanthanum in terms of lanthana, weight content in the carrier is 3%.

It weighs appropriate zinc nitrate to be dissolved in deionized water, the modified Hydrogen of above-mentioned lanthanum is carried on using equi-volume impregnating Catalyst precarsor ZnO/La-ZSM-5 is made in ZSM-5 molecular sieve carrier, 120 DEG C of dry 4h, 500 DEG C of roasting 4h.By 5g catalyst Precursor is placed in continuous fixed bed reactor, handles catalyst precarsor, bromine first using the mixed gas of bromomethane and nitrogen Alkane volumetric concentration is 80%, and treatment conditions are 250 DEG C, 0.3MPa(absolute pressure), 300h^-1, time 2h, obtained bromomethane preparing isobutene Catalyst is denoted as D-2.Catalyst weight group is obtained as ZnBr₂Weight content is 30%, ZnO in terms of oxide in terms of bromide Weight content is 4%, and 450 DEG C or less total acid contents are 0.8mmol/g in catalyst, 250 DEG C -350 DEG C of acid content account for 450 DEG C with The 56.2% of lower total acid content.

Bromomethane conversion preparing isobutene reaction carries out in continuous flow actuating miniature fixed bed reactors.Catalyst loading 5g, Unstripped gas is bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure For 2MPa(absolute pressure), air speed 200h^-1.After stable reaction one hour, sampling analysis.Reaction result is shown in Table 1.

Comparative example 3

Weigh appropriate lanthanum nitrate and PVP(K30) it is dissolved in deionized water, Hydrogen ZSM- is carried on using equi-volume impregnating 5 molecular sieve carriers (silica alumina ratio 50, Kong Rongwei 0.23ml/g, specific surface area 426m²/ g, bar shaped, equivalent diameter 1.5mm), it is quiet 6h, 100 DEG C of dry 9h are set, 600 DEG C of roasting 6h are risen to the heating rate of 1 DEG C/min, the modified Hydrogen ZSM-5 molecule of lanthanum is made Carrier is sieved, for lanthanum in terms of lanthana, weight content in the carrier is 3%.

It weighs appropriate zinc nitrate to be dissolved in deionized water, the modified Hydrogen of above-mentioned lanthanum is carried on using equi-volume impregnating ZSM-5 molecular sieve carrier, the dry 4h of 80 DEG C of nitrogen atmospheres, 500 DEG C of nitrogen atmospheres roast 4h, catalyst Z nBr are made₂/Mg- ZSM-5 is denoted as D-3.Catalyst weight group is obtained as ZnBr₂Weight content is 30% in terms of bromide, 450 DEG C in catalyst Following total acid content is 0.97mmol/g, and 250 DEG C -350 DEG C of acid content accounts for the 73.3% 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 bromomethane and nitrogen mixed gas, and wherein bromomethane volume content is 70%, and reaction temperature is 230 DEG C, reaction pressure For 2MPa(absolute pressure), air speed 200h^-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen and nitrogen, 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 92.78%.After stable reaction one hour, sampling point Analysis.Reaction result is shown in Table 1.

1 catalyst reaction performance of table

Claims (29)

1. a kind of using lanthanum modified zsm-5 zeolite as the preparation method of the preparing isobutene catalyst of carrier, it is characterised in that: including Following steps:

(1) lanthanum salt solution impregnation Hydrogen ZSM-5 molecular sieve is used, the modified Hydrogen ZSM-5 molecular sieve carrier of lanthanum is obtained；

(2) zinc oxide is introduced to the modified Hydrogen ZSM-5 molecular sieve carrier of lanthanum；

(3) incomplete bromination processing is carried out to the lanthanum modified zsm-5 zeolite carrier after introducing zinc oxide；Bromination is into catalyst Zinc oxide weight content is 0.5%-20%, and zinc bromide weight content is 10%-50%.

2. according to the method described in claim 1, containing lanthanum salt and water soluble polymer it is characterized by: using in step (1) The aqueous solution incipient impregnation Hydrogen ZSM-5 molecular sieve carrier of polymer stands 4h-12h, 80 DEG C -120 DEG C dry 6h-12h, Under air atmosphere, 500 DEG C of -700 DEG C of roasting 4h-8h Hydrogen ZSM-s modified to get lanthanum are risen to 1 DEG C/min ~ 3 DEG C/min 5 molecular sieve carriers.

3. according to the method described in claim 2, it is characterized by: the lanthanum salt is lanthanum nitrate, lanthanum chloride, one in lanthanum sulfate Kind；The water soluble polymer is one or more of polyacrylamide or polyvinylpyrrolidone, high water solubility The mass ratio of Molecularly Imprinted Polymer and lanthanum is 2 ~ 5.

4. according to the method described in claim 3, it is characterized by: the lanthanum salt is lanthanum nitrate；The water soluble polymer is poly- Conjunction object is polyvinylpyrrolidone.

5. according to the method described in claim 3, it is characterized by: zinc oxide is introduced to lanthanum modified hydrogen ZSM-5 in step (2) Molecular sieve carrier uses infusion process.

6. according to the method described in claim 5, it is characterized by: impregnate modified carrier using zinc solution, and carrying out Dry, roasting.

7. according to the method described in claim 6, it is characterized by: 60 DEG C -150 DEG C of drying temperature, time 1h-24h；Roasting 300 DEG C -800 DEG C of temperature, time 1h-24h.

8. according to the method described in claim 7, it is characterized by: 80 DEG C -120 DEG C of drying temperature, time 4h-8h；Roasting 400 DEG C -600 DEG C of temperature, time 4h-8h.

9. according to the method described in claim 6, it is characterized by: zinc salt is nitrate, hydrochloride, acetate, citrate One or more of.

10. according to the method described in claim 1, it is characterized by: bromination processing in step (3), refers to brominated using gas phase Compound handles the sample of load zinc oxide.

11. according to the method described in claim 10, it is characterized by: bromine-containing compound refers to bromomethane, methylene bromide, tribromo One or more of methane.

12. according to the method described in claim 10, it is characterized by: using gas phase bromine-containing compound and inert gas mixing Gas carries out bromination processing, and when being handled using mixed gas bromination, bromomethane volumetric concentration is not less than 20%.

13. according to the method described in claim 10, it is characterized by: specific bromination process is as follows: the sample of zinc oxide will be loaded Product are placed in continuous fixed bed reactor, and 150 DEG C -400 DEG C are warming up under inert atmosphere, are passed through gas phase bromine-containing compound gas Body, gas space velocity 50h^-1-1000 h^-1；System pressure is 0.1MPa-0.5MPa, and the processing time is 0.5h-8h.

14. according to the method for claim 13, it is characterised in that: be warming up to 180 DEG C -350 DEG C under inert atmosphere, be passed through gas Phase bromine-containing compound gas, gas space velocity 100h^-1-500h^-1；System pressure is 0.1MPa-0.3MPa, and the processing time is 1h- 4h。

15. a kind of catalyst prepared using claim 1 to 14 either method, it is characterised in that: catalyst is by zinc oxide, bromine Change the Hydrogen ZSM-5 molecular sieve carrier composition that zinc and lanthanum are modified, based on the weight content of catalyst, zinc oxide content 0.5%- 20%, bromination Zn content is 10%-50%, and the modified Hydrogen ZSM-5 molecular sieve vector contg of lanthanum is 40%-85%, what the lanthanum was modified In Hydrogen ZSM-5 molecular sieve carrier, weight content of the lanthanum in terms of lanthana in the carrier is 1%-5%, and Hydrogen ZSM-5 molecular sieve carries Body silica alumina ratio is 20 ~ 200.

16. catalyst according to claim 15, it is characterised in that: zinc oxide content 1%-15%, bromination Zn content are 10%-45%, the modified Hydrogen ZSM-5 molecular sieve vector contg of lanthanum are 50%-85%, Hydrogen ZSM-5 molecular sieve carrier sial mole Than being 20 ~ 150.

17. catalyst according to claim 15, it is characterised in that: 450 DEG C or less total acid contents are in catalyst 0.5mmol/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.

18. catalyst according to claim 17, it is characterised in that: 450 DEG C or less total acid content 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.

19. catalyst according to claim 18, it is characterised in that: 450 DEG C or less total acid content 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.

20. the application of catalyst described in claim 15, it is characterised in that: including carrying out hydrogen reducing activation to catalyst, make Content of halogen in catalyst is the 20%-90% for restoring total halogen content in procatalyst, then makes halide and above-mentioned hydrogen Catalyst contact after gas reduction activation, to prepare isobutene.

21. the application of the catalyst according to claim 20, it is characterised in that: the condition of hydrogen reducing activation makes catalyst In content of halogen be restore procatalyst in total halogen content 30%-80%.

22. the application of the catalyst according to claim 20, it is characterised in that: the mode of hydrogen reducing activation is included in inertia By catalyzer temperature-elevating to 300 DEG C -600 DEG C under atmosphere；Then passing to air speed is 200h^-1-2000h^-1Hydrogen or hydrogen and inertia The mixed gas of gas keeps 2h-16h in 0.1MPa-0.5MPa, and hydrogen volume percentage composition is 10%-95% in mixed gas.

23. the application of the catalyst according to claim 22, it is characterised in that: be warming up to 350 DEG C -550 DEG C；Then pass to sky Speed is 500h^-1-1000h^-1Hydrogen or hydrogen and inert gas mixed gas, 0.1MPa-0.3MPa keep 4h-8h, institute Stating hydrogen volume percentage composition in mixed gas is 30%-90%.

24. the application of the catalyst according to claim 20, it is characterised in that: halide is a halide, dihalo One of methane, three halides are a variety of.

25. the application of the catalyst according to claim 20, it is characterised in that: halide is bromomethane, methylene bromide, three One of bromomethane is a variety of.

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

27. the application of the catalyst according to claim 26, it is characterised in that: reaction temperature is 180 DEG C -300 DEG C；Reaction pressure Power is 0.1MPa-3MPa；Air speed is 200h^-1-500h^-1。

28. the application of the catalyst according to claim 20, it is characterised in that: including under inert atmosphere by catalyzer temperature-elevating extremely 300 DEG C -600 DEG C, then passing to air speed is 200h^-1-2000h^-1Hydrogen or hydrogen and inert gas mixed gas, 0.1MPa-0.5MPa handles 2h-16h, is down to reaction temperature and is passed through halide and is reacted, hydrogen volume percentage in gaseous mixture Content is 10%-95%.

29. the application of catalyst according to claim 28, it is characterised in that: including under inert atmosphere by catalyzer temperature-elevating extremely 350℃-550℃；Then passing to air speed is 500h^-1-1000h^-1Hydrogen or hydrogen and inert gas mixed gas, After 0.1MPa-0.3MPa handles 4h-8h, it is down to reaction temperature and is passed through halide and reacted, hydrogen volume hundred in gaseous mixture Dividing content is 30%-90%.