CN106140231A - A kind of alkali-earth metal modified loaded catalyst and its preparation method and application - Google Patents
A kind of alkali-earth metal modified loaded catalyst and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of alkali-earth metal modified loaded catalyst and its preparation method and application.Described catalyst is made up of zinc oxide, zinc halide, alkaline earth oxide, alumina support, and based on the weight content of catalyst, zinc oxide content is 0.5%-20%；Zinc halide content is 10%-50%；Alkaline earth oxide meter content is 0.1%-20%；Surplus is carrier.The preparation method of above-mentioned catalyst, comprises the steps: that (1) uses co-impregnation zinc element presoma and alkaline earth precursor to be carried on carrier, prepares catalyst precarsor after drying, roasting；(2) step (1) gained catalyst precarsor is carried out halogenation treatment；Prepare loaded catalyst.This catalyst can significantly improve the selectivity of isobutene. for the reaction of bromomethane preparing isobutene.
Description
Technical field
The present invention relates to a kind of alkali-earth metal modified loaded catalyst and its preparation method and application, relate in particular to a kind of alkali-earth metal modified halide preparing isobutene catalyst and its preparation method and application.
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, and consumption structure is diversified trend.Multiple high value-added product can be prepared for raw material, such as: multiple Organic Chemicals and the fine chemistry products such as butyl rubber, polyisobutylene, methyl tertiary butyl ether(MTBE), isoprene and lucite with isobutene..Owing to the market scale of isobutene. downstream product constantly expands, its imbalance between supply and demand will gradually highlight, and particularly under the background of petroleum resources exhaustion day by day, isobutene. yield has become the critical bottleneck of restriction downstream industry development.Therefore, the isobutene. syntheti c route of exploitation non-petroleum base, extremely the most urgent.
Methane is the main component of natural gas, the important research content during therefore methane trans-utilization just becomes gas chemical industry's technology.The most in recent years, develop fast development at shale gas, if it is possible to produce isobutene. from methane, an important approach will be provided for obtaining isobutene..But methane stable in properties, the most easily-activated, become the bottleneck of methane chemical utilization.Both at home and abroad many researcheres carry out methane activation, Study on Transformation one after another, among these, methane transformation technology again after halogen functional groupization, it is expected to become an important breakthrough mouth of a solution methane transformation technology difficult problem.
Bromomethane is important methane halides, can the many chemical products of preparation from bromomethane.Chinese patent CN
101041609A, CN 101284232A discloses one by methane at oxygen and HBr/H2Being converted into bromomethane under the effect of O, then bromomethane reacts the method generating C3 ~ C13 mixing high-carbon hydrocarbon further, and the hydrocarbon selective of more than C5 is 70%.Wherein, HBr for methane bromination, then discharges in first reactor in second reactor, recovered after be used further in back reaction, it is achieved the recycling of HBr.(CN 102527427A, the Jieli such as Wang Ye
He, Ting Xu, Zhihui Wang, et.al. Angew. Chem. Int. Ed. 2012,51,2438-2442) modified molecular sieve catalyst disclosing a kind of halide propylene and preparation method thereof.By using fluorochemical moditied processing molecular sieve, obtaining a kind of containing appropriate microporous structure and the catalyst of acidity, this catalyst can effectively be catalyzed halide and be converted into the reaction of propylene.Prepared catalyst one way bromomethane conversion ratio in the reaction that bromomethane is preparing propylene transformed is 35 ~ 99%, and the selectivity of propylene is 27 ~ 70%；In the reaction that chloromethanes is preparing propylene transformed, one way methyl chloride conversion rate is 30 ~ 99%, and the selectivity of propylene is 15 ~ 70%.Ivan M. Lorkovic et al. (Ivan M. Lorkovic, Aysen Yilmaz, Gurkan A. Yilmaz, et al.
Catalysis Today, 2004,98,317-322) it is also proposed that generate bromo-hydrocarbons with bromine with the alkane reaction in natural gas, then on metal oxide catalyst, bromo-hydrocarbons is converted into dimethyl ether, methanol and metal bromide, obtain metal-oxide after metal bromide oxygen recovery and discharge simple substance bromine, completing the circulation of bromine.
At present, it is mainly methanol and dimethyl ether about purpose product in the existing document that halide converts, additionally also have acetic acid, higher hydrocarbons, ethylene and propylene, and in the technology with alkene as target product, product mostly is ethylene, propylene, and single selectivity of product is the highest, and not yet find the relevant report of bromomethane high selectivity isobutene..
Summary of the invention
According to the deficiencies in the prior art, the present invention provides a kind of alkali-earth metal modified halide preparing isobutene catalyst and its preparation method and application.
A kind of alkali-earth metal modified loaded catalyst, described catalyst is made up of zinc oxide, zinc halide, alkaline earth oxide, alumina support, and based on the weight content of catalyst, zinc oxide content is 0.5%-20%, preferably 1%-15%, further preferred 1%-9%；Zinc halide content is 10%-50%, preferably 15%-45%, further preferred 18%-39%；Alkaline earth oxide meter content is 0.1%-20%, preferably 0.1%-15%, more preferably 0.5%-5%, and surplus is carrier.
One or more during zinc halide includes zinc fluoride, zinc chloride, zinc bromide, zinc iodide described in above-mentioned catalyst, preferably zinc bromide.Described alkaline-earth metal includes one or more in the elements such as Be, Mg, Ca, Sr, Ba, Ra, preferably one or more in the metal such as Mg, Ca, Ba, further preferred barium.
The preparation method of above-mentioned catalyst, comprises the steps:
(1) use co-impregnation zinc element presoma and alkaline earth precursor to be carried on carrier, after drying, roasting, prepare catalyst precarsor；
(2) step (1) gained catalyst precarsor is carried out halogenation treatment；Prepare loaded catalyst.
The inventive method, described in step (1), zinc element presoma and alkaline earth precursor are inorganic salt or organic salt, preferably nitrate, sulfate, hydrochlorate, acetate, citrate, more preferably nitrate.
The inventive method, step (1) baking temperature is 50 DEG C-200 DEG C, preferably 60 DEG C-150 DEG C, more preferably 80 DEG C-120 DEG C；Drying time is 1h-48h, preferably 2h-36h, more preferably 2h-24h；Can be vacuum drying time dry, it is also possible to for being dried under the conditions of inert gas shielding, it is also possible to be dried in air atmosphere；Sintering temperature is 200 DEG C-800 DEG C, preferably 300 DEG C-600 DEG C, more preferably 350 DEG C-500 DEG C；Roasting time is 1h-24h, preferably 2h-16h, more preferably 4h-8h；Can be to be dried under the conditions of inert gas shielding during roasting, it is also possible to be dried in air atmosphere.
The inventive method, halogenation treatment described in step (2), refer to use gas phase halogen contained compound that the sample of load zinc oxide is processed.Halogen contained compound refers to one or more in a halide, methylene halide, three halides, preferably one halide, more preferably one bromomethane.Gas phase halogen contained compound can also be used to carry out halogenation treatment with the mixed gas of noble gas, and when using mixed gas halogenation treatment, halide volumetric concentration is not less than 20%, preferably not less than 30%.Concrete halogenation process is as follows: be placed in continuous fixed bed reactor by the sample of load zinc oxide, 150 DEG C-400 DEG C it are warming up under inert atmosphere, preferably 180 DEG C-350 DEG C, more preferably 200 DEG C-300 DEG C, being passed through gas phase halogen contained compound gas, gas space velocity is 50h-1-1000 h-1, preferably 100h-1-500h-1；Can carry out at normal pressure during process, it is also possible to carry out under a certain pressure, system pressure is 0.1MPa-0.5MPa(absolute pressure), preferably 0.1MPa-0.3MPa(absolute pressure), the process time is 0.5h-8h, preferably 1h-4h.
The application in halide preparing isobutene of the above-mentioned loaded catalyst, with halide as raw material, reaction temperature is 150 DEG C-350 DEG C, preferably 180 DEG C-300 DEG C, more preferably 200 DEG C-270 DEG C；Reaction pressure is 0.1MPa-5MPa(absolute pressure), preferably 0.1MPa-3MPa(absolute pressure)；Air speed is 50h-1-1000h-1, preferably 200h-1-500h-1, needing catalyst is carried out activation processing before charging, the content of halogen activated to catalyst is the 20%-90%, preferably 30%-80%, further preferred 40%-80% of total halogen content in reduction procatalyst.
In above-mentioned application, a kind of concrete activated process is as follows: by catalyzer temperature-elevating to 300 DEG C-600 DEG C under inert atmosphere, preferably 350 DEG C-550 DEG C；Then passing to air speed is 200h-1-2000h-1, preferably 500h-1-1000h-1Hydrogen or the mixed gas of hydrogen and noble gas, in 0.1MPa-0.5MPa(absolute pressure), preferably 0.1MPa-0.3MPa(absolute pressure), after processing 2h-16h, preferably 4h-8h, be down to reaction temperature and be passed through halide and react.In described gaseous mixture, hydrogen volume percentage composition is 10%-95%, preferably 30%-90%, more preferably 50%-90%.
In above-mentioned application, raw material can also be the mixed gas of halide and noble gas, and in mixed gas, the volumetric concentration of halide is 10%-90%, preferably 30%-80%.
Noble gas involved in above-mentioned application is the gas that nitrogen, argon, helium etc. do not occur chemical reaction under the conditions of involved in the present invention, preferably nitrogen.
In above-mentioned application, halide raw material can be a halide, methylene halide, three halides, preferably one bromomethane, methylene bromide, bromoform, more preferably one bromomethane.
In above-mentioned application, the reaction of halide preparing isobutene can be carried out, such as fixed bed, fluid bed, fixed fluidized bed, moving bed, the reactor of the form such as slurry bed system or ebullated bed, preferably fixed bed, fluidized-bed reactor in existing any form reactor.
Compared with prior art, bromomethane height can be optionally converted into isobutene. by the method that the present invention relates to.Halide produces the reactive intermediate of CHx form in course of reaction by cracking, reacts without enough active center, and this reactive intermediate will accumulate formation carbon distribution on catalyst surface, makes catalysqt deactivation.After adding alkali metal promoter, can the concentration of dilute catalyst Active sites to a certain extent, and distribution is more uniform, the reactive intermediate of CHx form can be converted into isobutene. product in time, thus improve the activity of catalyst, also reach to reduce the purpose of carbon distribution.The present invention relates to bromomethane conversion preparing isobutene method for preparing catalyst simple, it is easy to industrialization.Bromomethane of the present invention converts preparing isobutene method and has reaction condition gentleness, selectivity of product advantages of higher, easily realizes industrialization, and application prospect is boundless.
Detailed description of the invention
Further illustrate technology contents and the effect of the present invention below in conjunction with embodiment, but be not intended to the present invention.
Embodiment
1
Preparation, containing zinc nitrate and the aqueous solution of beryllium nitrate, uses equi-volume impregnating to be carried on alumina support, and 100 DEG C of dry 8h, 500 DEG C of roasting 4h prepare catalyst precarsor.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr2Content is 30%, and ZnO content is 4%, and Be content in terms of oxide is 0.5%.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 50%, and reaction temperature is 230 DEG C, and reaction pressure is 1MPa(absolute pressure), air speed is 500h-1, it is passed through unstripped gas procatalyst and activates in a hydrogen atmosphere, reducing condition is 400 DEG C, 0.2MPa(absolute pressure), 1000h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 65.28%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio is 92.51%, and selective isobutene is 75.33%, and carbon deposition quantity is 0.62%.
Embodiment
2
Preparation, containing zinc nitrate and the aqueous solution of magnesium nitrate, uses equi-volume impregnating to be carried on alumina support, and aged at room temperature 4h, 80 DEG C of dry 12h, 360 DEG C of roasting 10h prepare catalyst precarsor.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr2Content is 30%, and ZnO content is 4%, and Mg content in terms of oxide is 0.5%.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 51.7%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio is 97.05%, and selective isobutene is 82.35%, and carbon deposition quantity is 0.41%.
Embodiment
3
(pore volume is 0.71ml/g, and specific surface area is 236m to take 10g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm), accounting for catalyst weight according to Zn, Ca and be respectively 15%, 0.5%, surplus is that the proportioning preparation of aluminium oxide is carried on alumina support containing zinc nitrate and the aqueous solution of calcium nitrate, employing equi-volume impregnating, aged at room temperature 4h, 120 DEG C of dry 6h, 400 DEG C of roasting 6h, prepare catalyst precarsor.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr2Content is 30%, and ZnO content is 4%, and Ca content in terms of oxide is 0.5%.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 80%, and reaction temperature is 200 DEG C, and reaction pressure is 3MPa(absolute pressure), air speed is 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 50%, and reducing condition is 500 DEG C, 0.1MPa(absolute pressure), 500h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 45.66%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio is 97.92%, and selective isobutene is 82.64%, and carbon deposition quantity is 0.39%.
Embodiment
4
(pore volume is 0.71ml/g, and specific surface area is 236m to take 10g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm), accounting for catalyst weight according to Zn, Sr and be respectively 15%, 0.5%, surplus is that the proportioning preparation of aluminium oxide is carried on alumina support containing zinc nitrate and the aqueous solution of strontium nitrate, employing equi-volume impregnating, aged at room temperature 4h, 90 DEG C of dry 12h, 450 DEG C of roasting 5h, prepare catalyst precarsor.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr2Content is 30%, and ZnO content is 4%, and Sr content in terms of oxide is 0.5%.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 30%, and reaction temperature is 270 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 70%, and reducing condition is 350 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 6h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 55.9%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio is 96.64%, and selective isobutene is 76.81%, and carbon deposition quantity is 0.45%.
Embodiment
5
(pore volume is 0.71ml/g, and specific surface area is 236m to take 10g aluminium oxide2/ g, bar shaped, equivalent diameter 1.5mm), accounting for catalyst weight according to Zn, Ba and be respectively 15%, 0.5%, surplus is that the proportioning preparation of aluminium oxide is carried on alumina support containing zinc nitrate and the aqueous solution of barium nitrate, employing equi-volume impregnating, aged at room temperature 4h, 120 DEG C of dry 4h, 350 DEG C of roasting 8h, prepare catalyst precarsor.Using continuous fixed bed reactor, process catalyst precarsor under mixed atmosphere, wherein monobromo methane volumetric content is 30%, and surplus is nitrogen, and treatment conditions are 230 DEG C, 0.1MPa, 100h-1, the time is 4h.Prepare halide preparing isobutene catalyst, in terms of weight content, ZnBr2Content is 30%, and ZnO content is 4%, and Ba content in terms of oxide is 0.5%.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane, and reaction temperature is 270 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 60%, and reducing condition is 550 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 8h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 40%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio is 98.11%, and selective isobutene is 84.23%, and carbon deposition quantity is 0.22%.
Embodiment
6
Catalyst is prepared with embodiment 5, and difference is, Ba content in terms of oxide is 2%.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 50%, and reaction temperature is 230 DEG C, and reaction pressure is 0.1MPa(absolute pressure), air speed is 500h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), 1000h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 56.46%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio is 98.85%, and selective isobutene is 68.32%.
Embodiment
7
Catalyst is prepared with embodiment 5, and difference is, Ba content in terms of oxide is 5%.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 80%, and reaction temperature is 200 DEG C, and reaction pressure is 3MPa(absolute pressure), air speed is 350h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 90%, and reducing condition is 500 DEG C, 0.1MPa(absolute pressure), 500h-1, recovery time 6h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 50.22%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio is 99.48%, and selective isobutene is 58.73%.
Embodiment
8
Catalyst is prepared with embodiment 5, and difference is, Ba content in terms of oxide is 10%.
Bromomethane converts preparing isobutene reaction to be carried out in flowing micro fixed-bed reactor continuously.Catalyst loading amount 5g, unstripped gas is a bromomethane and nitrogen mixed gas, and wherein monobromo methane volumetric content is 70%, and reaction temperature is 230 DEG C, and reaction pressure is 2MPa(absolute pressure), air speed is 200h-1.Before being passed through unstripped gas, catalyst activates under the mixed atmosphere of hydrogen, and in mixed gas, hydrogen volume content is 80%, and reducing condition is 450 DEG C, 0.3MPa(absolute pressure), 800h-1, recovery time 4h, reduction rear catalyst in content of halogen be reduction procatalyst in total halogen content 37.84%.After stable reaction one hour, sampling analysis.Bromomethane conversion ratio is 99.65%, and selective isobutene is 48.17%.
Comparative example
1
Catalyst is prepared with embodiment 5, and difference is, does not carries out halogenation treatment.Evaluating catalyst method is with embodiment 5, and bromomethane conversion ratio is 99.27%, and selective isobutene is 0%.
Comparative example
2
Catalyst is prepared with embodiment 5, and evaluating catalyst method is with embodiment 5, and difference is, does not carries out activation processing.Bromomethane conversion ratio is 3.31%, and selective isobutene is 0%.
Comparative example
3
Catalyst is prepared with embodiment 5, and difference is in activation process that by zinc bromide Restore All are zinc.Evaluating catalyst method is with embodiment 5, bromomethane conversion ratio 0.85%, selective isobutene 0%.
Claims (22)
1. an alkali-earth metal modified loaded catalyst, it is characterised in that: described catalyst is made up of zinc oxide, zinc halide, alkaline earth oxide, alumina support, and based on the weight content of catalyst, zinc oxide content is 0.5%-20%；Zinc halide content is 10%-50%；Alkali-metal-oxide content is 0.1%-20%, and surplus is carrier.
Catalyst the most according to claim 1, it is characterised in that: based on the weight content of catalyst, zinc oxide content is 1%-15%；Zinc halide content is 15%-45%；Alkaline earth oxide meter content is 0.1%-15%.
Catalyst the most according to claim 2, it is characterised in that: zinc oxide content is 1%-9%；Zinc halide content is 18%-39%；Alkaline earth oxide meter content is 0.5%-5%.
Catalyst the most according to claim 1, it is characterised in that: described zinc halide includes one or more in zinc fluoride, zinc chloride, zinc bromide, zinc iodide；Described alkaline-earth metal includes one or more in Be, Mg, Ca, Sr, Ba, Ra.
Catalyst the most according to claim 4, it is characterised in that: described zinc halide is zinc bromide；Described alkaline-earth metal includes one or more in Mg, Ca, Ba.
6. the preparation method of the arbitrary catalyst of claim 1 to 5, it is characterised in that: comprise the steps:
(1) use co-impregnation zinc element presoma and alkaline earth precursor to be carried on carrier, after drying, roasting, prepare catalyst precarsor；
(2) step (1) gained catalyst precarsor is carried out halogenation treatment；Prepare loaded catalyst.
Method the most according to claim 6, it is characterised in that: in step (1), zinc precursor and alkaline earth precursor are one or more in nitrate, sulfate, hydrochlorate, acetate, citrate.
Method the most according to claim 6, it is characterised in that: baking temperature 50 DEG C-200 DEG C in step (1)；Drying time is 1h-48h；Sintering temperature is 200 DEG C-800 DEG C；Roasting time is 1h-24h.
Method the most according to claim 8, it is characterised in that: baking temperature is 60 DEG C-150 DEG C；Drying time is 2h-36h；Sintering temperature is 300 DEG C-600 DEG C；Roasting time is 2h-16h.
Method the most according to claim 6, it is characterised in that: halogenation treatment described in step (2) refers to use gas phase halogen contained compound to process the sample of load zinc oxide.
11. methods according to claim 10, it is characterised in that: halogen contained compound refers to one or more in a halide, methylene halide, three halides.
12. methods according to claim 6, it is characterised in that: using gas phase halogen contained compound to carry out halogenation treatment with the mixed gas of noble gas in step (2), halide volumetric concentration is not less than 20%.
13. methods according to claim 6, it is characterized in that: in step (2), halogenation process is as follows: the sample of load zinc oxide is placed in continuous fixed bed reactor, being warming up to 150 DEG C-400 DEG C under inert atmosphere, be passed through gas phase halogen contained compound gas, gas space velocity is 50h-1-1000
h-1；System pressure is 0.1MPa-0.5MPa, and the process time is 0.5h-8h.
14. methods according to claim 13, it is characterised in that: being warming up to 180 DEG C-350 DEG C under inert atmosphere, be passed through gas phase halogen contained compound gas, gas space velocity is 100h-1-500h-1；System pressure is 0.1MPa-0.3MPa(absolute pressure), the process time is 1h-4h.
Catalyst application in preparing isobutene described in 15. claim 1, it is characterised in that: with halide as raw material, reaction temperature is 150 DEG C-350；Reaction pressure is 0.1MPa-5MPa；Air speed is 50h-1-1000h-1, needing catalyst is carried out activation processing before charging, the content of halogen activated to catalyst is the 20%-90% of total halogen content in reduction procatalyst.
16. application according to claim 15, 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, needing catalyst is carried out activation processing before charging, the content of halogen activated to catalyst is the 30%-80% of total halogen content in reduction procatalyst.
17. application according to claim 15, it is characterised in that: activated process is as follows: by catalyzer temperature-elevating to 350 DEG C-550 DEG C under inert atmosphere；Then passing to air speed is 200h-1-2000h-1Hydrogen or the mixed gas of hydrogen and noble gas, after 0.1MPa-0.5MPa processes 2h-16h, be down to reaction temperature and be passed through halide and react, in described gaseous mixture, hydrogen volume percentage composition is 10%-95%.
18. application according to claim 17, it is characterised in that: by catalyzer temperature-elevating to 350 DEG C-550 DEG C under inert atmosphere；Then passing to air speed is 500h-1-1000h-1Hydrogen or the mixed gas of hydrogen and noble gas, after 0.1MPa-0.3MPa processes 4h-8h, be down to reaction temperature and be passed through halide and react, in described gaseous mixture, hydrogen volume percentage composition is 30%-90%.
19. application according to claim 15, it is characterised in that: raw material is the mixed gas of halide and noble gas, and in mixed gas, the volumetric concentration of halide is 10%-90%.
20. application according to claim 15, it is characterised in that: halide raw material is one or more in a halide, methylene halide, three halides.
21. application according to claim 15, it is characterised in that: halide raw material is one or more in a bromomethane, methylene bromide, bromoform.
22. application according to claim 15, it is characterised in that: the reaction of halide preparing isobutene is carried out in fixed bed, fluid bed, fixed fluidized bed, moving bed, slurry bed system or fluidized bed reactor.
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| CN111151287A (en) * | 2020-01-17 | 2020-05-15 | 厦门大学 | Alkaline oxide modified boron nitride catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111151287A (en) * | 2020-01-17 | 2020-05-15 | 厦门大学 | Alkaline oxide modified boron nitride catalyst and preparation method and application thereof |
| CN111151287B (en) * | 2020-01-17 | 2021-12-03 | 厦门大学 | Alkaline oxide modified boron nitride catalyst and preparation method and application thereof |
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