CN109745989A - oxychlorination catalyst and its preparation method and application - Google Patents
oxychlorination catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN109745989A CN109745989A CN201711065213.2A CN201711065213A CN109745989A CN 109745989 A CN109745989 A CN 109745989A CN 201711065213 A CN201711065213 A CN 201711065213A CN 109745989 A CN109745989 A CN 109745989A
- Authority
- CN
- China
- Prior art keywords
- oxychlorination
- coating
- carrier
- catalyst
- oxychlorination catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
Abstract
The present invention provides a kind of oxychlorination catalysts and its preparation method and application.Oxychlorination catalyst provided by the invention includes monolithic substrate, coating, active component and adjuvant component, wherein the monolithic substrate is ceramic material, and the ceramic material is selected from least one of corundum, cordierite, mullite, zirconium oxide, titanium dioxide, silicon carbide, aluminium titanates and magnesium silicate.Oxychlorination catalyst provided by the invention is applied to ethylene oxychlorination, has obtained excellent activity, and overcome prior art and wear big disadvantage.
Description
Technical field
The present invention relates to a kind of oxychlorination catalysts and its preparation method and application.
Background technique
Ethylene and oxygen, hcl reaction generate 1,2- dichloroethanes, commonly referred to as dichloroethanes (EDC), are a kind of works
The compound of millions of tons is produced in industry every year, is converted into vinyl chloride and hydrogen chloride after compound cracking, vinyl chloride monomer can
Polymerization becomes the polyvinyl chloride (PVC) for having extensive use.For many years, the whole world has been developed through oxychlorination process and has been produced
The Catalyst And Method of chlorohydrocarbon, and large-scale application has been carried out on commercial plant.Currently, not according to raw material route
Together, industrially use two different production methods: one is B.F.Goodrich companies, the U.S. for the air method of representative, the party
Method is to carry out oxi-chlorination by raw material of air, ethylene and hydrogen chloride, and another kind is to be with Mitsui Dong Ya Co., Ltd.
The oxygen method of representative, this method carry out oxi-chlorination by raw material of pure oxygen, ethylene and hydrogen chloride.Chlorine is being produced with process for oxychlorination
During hydrocarbon, catalyst successfully applies many years.
Oxi-chlorination is passed usually using fluidized bed or fixed-bed process, but since this reaction is exothermic reaction for guarantee
Heat more evenly, advantageously using fluidized-bed process, i.e., in a fluidized bed by the mixing of ethylene, hydrogen chloride and oxygen or oxygen-containing gas
Object carries out gas phase reaction.But the particle that fluidized bed main problem is the catalyst of fluidisation will cause the abrasion of catalyst and right
The abrasion of reactor, and be possible to therefore and the parking that causes the accident, and therefore increase production cost.
Summary of the invention
For the situation of the prior art, the purpose of the present invention is to provide a kind of oxychlorination catalyst and preparation method thereof and
Using.Oxychlorination catalyst provided by the invention is applied to ethylene oxychlorination, has obtained excellent activity, and overcome existing
The big disadvantage of process wear.
In the first aspect, the present invention provides a kind of oxychlorination catalysts comprising monolithic substrate, coating, activity
Component and adjuvant component, wherein the monolithic substrate is ceramic material, the ceramic material is selected from corundum, cordierite, richness
At least one of mullite, zirconium oxide, titanium dioxide, silicon carbide, aluminium titanates and magnesium silicate.Preferably, of the invention to urge
Agent is made of monolithic substrate, coating, active component and adjuvant component.
According to the present invention, the oxychlorination catalyst is by the carrier of ceramic material, coating, active component and auxiliary agent group
The integral catalyzer being grouped as.
Embodiment according to the present invention, the ingredient of the coating include aluminium oxide or aluminium oxide-titanium oxide mixture.It is excellent
Selection of land, the coating are made of aluminium oxide-titanium oxide, and preferably the content of titanium oxide is 0-50wt%, preferably 2-20wt%.
Embodiment according to the present invention, the quality of the coating are the 1-20%, preferably 5- of the carrier quality
15%.
Embodiment according to the present invention, the active component are copper.
Embodiment according to the present invention, the active component content are calculated as 3-8wt%, preferably 4- with coating gross mass
7wt%.
Embodiment according to the present invention, the adjuvant component include, 0.1-10wt% selected from lanthanum, cerium, neodymium, praseodymium and
At least one alkali of at least one of rare earth metal of yttrium, one of the transition metal of 0.1-10wt% and 0.1-10wt%
Metal or alkaline-earth metal, the above mass percentage is on the basis of coating quality.
Embodiment according to the present invention, the adjuvant component are that rare earth metal is lanthanum and/or cerium, and the transition metal is
Zinc, the alkali or alkaline earth metal are potassium, sodium or magnesium.
In the second aspect, the present invention provides a kind of preparation methods of oxychlorination catalyst comprising following steps:
Step S1 provides the monolithic substrate of ceramic material；
Step S2 provides the colloid for being used to prepare coating；
Colloid described in S2 is carried on carrier described in S1, then dried by step S3, calcining, cated to obtain
Carrier；
Step S4 provides the mixed solution containing active component and adjuvant component；
Step S5, by cated carrier impregnation in the mixed solution, to obtain loading active component and auxiliary agent
The carrier of component；
Step S6, by carrier drying, the activation of the active component of the load and adjuvant component, to obtain the catalysis
Agent.
Embodiment according to the present invention, the monolithic substrate of ceramic material described in step S1 can by preparation or
Purchase obtains.Preferably, the ceramic material is selected from corundum, cordierite, mullite, zirconium oxide, titanium dioxide, carbonization
At least one of silicon, aluminium titanates and magnesium silicate.
Embodiment according to the present invention, colloid described in step S2 are aluminium ti-based coating colloid.
Preferably, the production method of the colloid is selected from one of following four: (1) preparing soluble titanium salting liquid A
With sodium aluminate solution B, and two kinds of solution are mixed, obtains co-precipitate, filter, washing.Then in sediment, nitre is added
Acid solution simultaneously adjusts pH value formation colloidal sol.(2) the nitric acid mixed solution of aluminium and titanium is used, and ammonium hydroxide is added, after forming precipitating, mistake
Then filter, washing are added nitric acid solution and adjust pH value formation colloidal sol.(3) sol-gel method is used, from Aluminum sol system
Standby colloidal sol.Process is as follows, according to stoichiometric ratio, prepares certain density titanium salt aqueous solution and 10wt% Aluminum sol.Strong
The two is mixed under stirring, stirs 0.5h.(4) soluble titanium salting liquid A and sodium aluminate solution B are prepared, and by two kinds of solution
Mixing, obtains co-precipitate, filters, and washs, dry, calcining.Then by powder mull and the ethyl alcohol and levulinic of 1:1 are dispersed in
In ketone mixed liquor, colloidal sol is made in presoma content about 10wt%, ball milling 10h.
Embodiment according to the present invention will use the method for dipping that colloidal sol is loaded to carrier up in step S3, so
Afterwards, dry, calcining calculates carrier quality increment.Drying means includes being not limited to spontaneously dry, low-temperature vacuum drying, program
The methods of heating drying, the drying condition more mitigated is more advantageous to the combination of catalyst coat, and drying temperature should be controlled 150
Degree Celsius or less.Low heating rate should be used to be heated when calcining, preferably heating rate is 0.5~8 degrees celsius/minute, is forged
Burning temperature is 500~1000 degrees Celsius.Carrier quality increment is finally calculated, mass incremental and coating layer thickness should carry out calculating and table
Sign.If not reaching requirement, this step should be repeated until increment is met the requirements.Run-of-the-mill increment should be vehicle weight
1.5~10wt%.
According to the present invention, mantoquita, alkali metal salt or alkali salt, rare earth metal salt, transition metal salt are used in step S4
Mixed solution is made by mixing with water.The mantoquita is preferably copper chloride.
According to the present invention, mantoquita, alkali metal salt or alkali salt, rare earth metal salt, transition metal salt are used in step S5
Solution impregnation steps S3 coating obtained carrier.It is preferable to use incipient impregnation methods to be operated.The present invention
The activity and selectivity that can be required according to the condition of production of catalyst, the flexible addition for determining adjuvant component in catalyst
Amount.It is preferred that copper content is 3-8wt% in final catalyst, adjuvant component content is the rare earth metal of 0.1-10wt%, 0.1-
The transition metal of 10wt% and the alkali or alkaline earth metal of 0.1-10wt%, the above mass percentage are with coating quality
Benchmark.
According to the present invention, drying means includes being not limited to spontaneously dry in step S6, low-temperature vacuum drying, temperature programming
Dry, the methods of normal drying, the drying condition more mitigated is more advantageous to the combination of catalyst coat, and drying temperature should control
At 150 degrees Celsius or less.
According to the present invention, integral catalyzer prepared by above-mentioned steps has good thermal stability.According to the present invention,
The test method of the thermal stability are as follows: sample is placed in Muffle furnace, 20min is roasted at 400 DEG C, is taken out in air
It is cooled to room temperature, then repeats a heat stability testing, finally weigh weight, calculate weightless dose rate, i.e., weightless quality accounts for
The mass percent of overall quality.
In the third aspect, the application the present invention provides the oxychlorination catalyst in ethylene oxychlorination.
Catalyst of the invention can be used for air method ethylene oxychlorination system.Typical ethylene oxychlorination
Operating condition is temperature: 210-230 DEG C, pressure 0.25-0.35MPa, feed gas molar ratio C2H4:HCl:O2=1:(1.8-
2.0):(0.5-0.6)。
By using oxychlorination catalyst of the invention, the hydrogen chloride conversion ratio of ethylene oxychlorination can achieve for
99.0% or more, oxycarbide content is 0.5~2% in tail gas.
Specific embodiment
The present invention is described in detail with reference to embodiments, but the present invention is not limited by following embodiments.
The test method of thermal stability are as follows: sample is placed in Muffle furnace, 20min is roasted at 400 DEG C, is taken out in sky
It is cooled to room temperature in gas, then repeats a heat stability testing, finally weigh weight, calculate weightless dose rate, i.e., weightless matter
Amount accounts for the mass percent of overall quality.
Embodiment 1
Prepare 250 mesh cordierite honeycomb ceramics, volume 50mm*50mm*50mm, as carrier in advance.Then it uses
30ml titanium tetrachloride solution A, 80g aluminium-hydroxide powder is added in 150ml sodium hydroxide solution at 100 degrees Celsius, is stirred, system
The sodium aluminate solution B for obtaining sodium hydroxide/aluminium oxide (weight ratio)=1.4~1.6, under conditions of room temperature, pH are 6.0-9.0
Carry out coprecipitation reaction.After precipitating, it is filtered washing drying, roasts, obtains containing 20wt% at 600 degrees Celsius after dry
The aluminium oxide-titanium oxide mixture of titanium oxide.Then mixture is ground to and is dispersed in the ethyl alcohol and acetylacetone,2,4-pentanedione of mass ratio 1:1
In mixed liquor, colloidal sol is made in presoma content about 20wt%, ball milling 10h.Colloidal sol is loaded on carrier using the method for dipping
It goes, is then dried in vacuo at 80 degrees celsius, 500 degree of temperature programming calcinings, 1 degrees celsius/minute of heating rate calculates after the completion
Carrier quality increment.Colloidal sol is supported on process on carrier and needs three times, and mass incremental is the 14wt% of vehicle weight.
Copper chloride, potassium chloride, cerium chloride, zinc chloride is soluble in water, and dipping is ready for the carrier of coating, and 120 is Celsius
Spend dry 2h.The catalyst of cupric 4wt%, cerium 1wt%, potassium 1.5wt%, zinc 1wt% are obtained, mass percentage is with coating
On the basis of quality.
Embodiment 2
The preparation manipulation of carrier and coating is same as Example 1.Copper chloride, potassium chloride, cerium chloride, zinc chloride are dissolved in water
In, dipping is ready for the carrier of coating, 120 degrees Celsius of dry 2h.Obtain cupric 4wt%, cerium 0.5wt%, potassium 2wt%, zinc
The catalyst of 1wt%, mass percentage is on the basis of coating quality.
Embodiment 3
The preparation manipulation of carrier and coating is same as Example 1.Copper chloride, potassium chloride, cerium chloride, zinc chloride are dissolved in water
In, dipping is ready for the carrier of coating, 120 degrees Celsius of dry 2h.Obtain cupric 5.5wt%, cerium 1wt%, potassium 1.5wt%,
The catalyst of zinc 1wt%, mass percentage is on the basis of coating quality.
Embodiment 3 '
The preparation manipulation of carrier and coating is same as Example 1.Copper chloride, potassium chloride, cerium chloride, zinc chloride are dissolved in water
In, dipping is ready for the carrier of coating, 120 degrees Celsius of dry 2h.Obtain cupric 1wt%, cerium 1wt%, potassium 1.5wt%, zinc
The catalyst of 1wt%, mass percentage is on the basis of coating quality.
Embodiment 3 "
The preparation manipulation of carrier and coating is same as Example 1.Copper chloride, potassium chloride, cerium chloride, zinc chloride are dissolved in water
In, dipping is ready for the carrier of coating, 120 degrees Celsius of dry 2h.Obtain cupric 10wt%, cerium 1wt%, potassium 1.5wt%, zinc
The catalyst of 1wt%, mass percentage is on the basis of coating quality.
Embodiment 4
The operating procedure of catalyst preparation is same as Example 1, and only the percentage composition of titanium oxide is changed to 1wt%.It obtains
The catalyst of cupric 4wt%, cerium 1wt%, potassium 1.5wt%, zinc 1wt%, mass percentage is on the basis of coating quality.
Embodiment 4 '
The operating procedure of catalyst preparation is same as Example 1, and only the percentage composition of titanium oxide is changed to 10wt%.It obtains
The catalyst of cupric 4wt%, cerium 1wt%, potassium 1.5wt%, zinc 1wt%, mass percentage is on the basis of coating quality.
Embodiment 4 "
The operating procedure of catalyst preparation is same as Example 1, and only the percentage composition of titanium oxide is changed to 0wt%.It obtains
The catalyst of cupric 4wt%, cerium 1wt%, potassium 1.5wt%, zinc 1wt%, mass percentage is on the basis of coating quality.
Embodiment 5
The operating procedure of catalyst preparation is same as Example 1, and it is five times that colloidal sol, which is supported on process on carrier to increase, quality
Increment is the 19wt% of vehicle weight.Obtain the catalyst of cupric 4wt%, cerium 1wt%, potassium 1.5wt%, zinc 1wt%, quality hundred
Divide content on the basis of coating quality.
Embodiment 6
Still using the cordierite carrier in embodiment 1, coating the preparation method is as follows: process is as follows, counted according to chemistry
Ratio is measured, certain density titanium salt aqueous solution and 17wt% Aluminum sol are prepared.The two is mixed under vigorous stirring, stirring 0.5h is obtained
To colloidal sol.Colloidal sol is loaded into carrier up using the method for dipping, is then dried in vacuo at 80 degrees celsius, 500 degree of programs
Heating calcining, 1 degrees celsius/minute of heating rate calculate carrier quality increment after the completion.Colloidal sol is supported on process needs on carrier
Three times, mass incremental is the 14wt% of vehicle weight.
Copper chloride, potassium chloride, cerium chloride, zinc chloride is soluble in water, and dipping is ready for the carrier of coating, and 120 is Celsius
Spend dry 2h.The catalyst of cupric 4wt%, cerium 1wt%, potassium 1.5wt%, zinc 1wt% are obtained, mass percentage is with coating
On the basis of quality.
Embodiment 7
Use ZrO2The monolithic substrate of material, other preparation processes are the same as embodiment 1.Obtain cupric 4wt%, cerium 1wt%,
The catalyst of potassium 1.5wt%, zinc 1wt%, mass percentage is on the basis of coating quality.
The catalyst that above-described embodiment is obtained carries out thermal stability experiment, and loads in the reactor, 220 degrees Celsius,
0.32MPa, feed gas molar ratio are C2H4:HCl:O2It is reacted under conditions of=1:1.8~2.0:0.5~0.6, is as a result seen
Table 1.
The evaluation response result of catalyst in 1 present invention of table
It is above-mentioned that exemplary embodiment is illustrated, it should not be construed as limiting the invention.Although having disclosed
Multiple exemplary embodiments, those skilled in the art are readily appreciated that possible various deformation in exemplary embodiment, and do not have
Have and inherently deviates novel teachings and advantage of the invention.Therefore, all these Amoebidas are included in such as claim
In defined the scope of the present invention.It is understood that aforementioned is the explanation to various exemplary embodiment, it is not limitation
The deformation and other exemplary embodiments of disclosed specific embodiments, open embodiment, it is therefore an objective to be contained in appended right and want
In the range asked.
Claims (10)
1. a kind of oxychlorination catalyst comprising monolithic substrate, coating, active component and adjuvant component, wherein described whole
Body formula carrier is ceramic material, and the ceramic material is selected from corundum, cordierite, mullite, zirconium oxide, titanium dioxide, carbon
At least one of SiClx, aluminium titanates and magnesium silicate.
2. oxychlorination oxychlorination catalyst according to claim 1, which is characterized in that the ingredient of the coating includes oxidation
Aluminium or aluminium oxide-titanium oxide mixture, the preferably content of titanium oxide are 0-50wt%, preferably 2-20wt%.
3. oxychlorination catalyst according to claim 2, which is characterized in that the quality of the coating is the carrier quality
1-20%, preferably 5-15%.
4. oxychlorination catalyst according to any one of claim 1-3, which is characterized in that the active component is copper.
5. oxychlorination catalyst described in any one of -4 according to claim 1, which is characterized in that in terms of coating gross mass, institute
Stating active component content is 3wt%-8wt%, preferably 4wt%-7wt%.
6. oxychlorination catalyst according to any one of claims 1-5, which is characterized in that the adjuvant component packet
It includes, the transition metal of at least one of rare earth metal selected from lanthanum, cerium, neodymium, praseodymium and yttrium of 0.1-10wt%, 0.1-10wt%
One of and 0.1-10wt% at least one alkali or alkaline earth metal, the above mass percentage is with coating quality
Benchmark.
7. oxychlorination catalyst according to claim 6, which is characterized in that the adjuvant component is that rare earth metal is lanthanum
And/or cerium, the transition metal are zinc, the alkali or alkaline earth metal is potassium, sodium or magnesium.
8. the preparation method of oxychlorination catalyst described in any one of -7 according to claim 1 comprising:
Step S1 provides the monolithic substrate of ceramic material；
Step S2 provides the colloid for being used to prepare coating；
Colloid described in step S2 is carried on monolithic substrate described in step S1, then dried by step S3, calcining, with
To cated carrier；
Step S4 provides the mixed solution containing active component and adjuvant component；
Step S5, by the cated carrier impregnation in the mixed solution, to obtain loading active component and auxiliary agent
The carrier of component；
Step S6, by carrier drying, the activation of the active component of the load and adjuvant component, to obtain the catalyst.
9. oxychlorination catalyst described in any one of -7 or oxychlorination according to claim 8 are urged according to claim 1
Application of the oxychlorination catalyst that the preparation method of agent obtains in ethylene oxychlorination.
10. application according to claim 9, which is characterized in that the operating condition of the ethylene oxychlorination is temperature:
210 DEG C -230 DEG C, pressure 0.25MPa-0.35MPa, feed gas molar ratio C2H4: HCl:O2=1:(1.8-2.0): (0.5-
0.6)。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711065213.2A CN109745989A (en) | 2017-11-02 | 2017-11-02 | oxychlorination catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711065213.2A CN109745989A (en) | 2017-11-02 | 2017-11-02 | oxychlorination catalyst and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109745989A true CN109745989A (en) | 2019-05-14 |
Family
ID=66398437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711065213.2A Pending CN109745989A (en) | 2017-11-02 | 2017-11-02 | oxychlorination catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109745989A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433102A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst with olefin oxychlorination function and preparation method and application thereof |
| CN116947473A (en) * | 2023-06-15 | 2023-10-27 | 国能无锡环保科技有限公司 | Method for improving wear resistance of denitration catalyst |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830566A (en) * | 2006-04-18 | 2006-09-13 | 天津大学 | Preparation method of copper-cerium catalyst coated on FeCrAl carrier |
| CN1911517A (en) * | 2001-04-20 | 2007-02-14 | 气体产品与化学公司 | Coated monolith substrate and catalysts |
| CN100998942A (en) * | 2006-01-10 | 2007-07-18 | 中国石油化工股份有限公司 | Ethylene oxychlorination catalyst and its preparation method and application |
| CN101269326A (en) * | 2007-03-21 | 2008-09-24 | 中国科学院大连化学物理研究所 | Monolith catalyst for benzene hydrogenation to cyclohexene and preparation method thereof |
| CN101497040A (en) * | 2008-02-03 | 2009-08-05 | 中国科学院大连化学物理研究所 | Integral catalyst for producing hydrogen dioxide solution as well as preparation and application thereof |
| CN102463125A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin oxychlorination catalyst, preparation method thereof and method for preparing dichloroethane |
| CN104368336A (en) * | 2013-08-14 | 2015-02-25 | 中国科学院大连化学物理研究所 | Monolithic catalyst for hydrogen peroxide production through pentylanthraquinone process and preparation method thereof |
| CN105392561A (en) * | 2013-07-17 | 2016-03-09 | 东曹株式会社 | Heterogeneous catalyst and catalyst system for manufacturing 1,2-dichloroethane |
| CN106732499A (en) * | 2016-12-12 | 2017-05-31 | 北京三聚环保新材料股份有限公司 | A kind of preparation method of the aluminum oxide film layer carrier of monoblock type methyl hydride combustion catalyst |
-
2017
- 2017-11-02 CN CN201711065213.2A patent/CN109745989A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1911517A (en) * | 2001-04-20 | 2007-02-14 | 气体产品与化学公司 | Coated monolith substrate and catalysts |
| CN100998942A (en) * | 2006-01-10 | 2007-07-18 | 中国石油化工股份有限公司 | Ethylene oxychlorination catalyst and its preparation method and application |
| CN1830566A (en) * | 2006-04-18 | 2006-09-13 | 天津大学 | Preparation method of copper-cerium catalyst coated on FeCrAl carrier |
| CN101269326A (en) * | 2007-03-21 | 2008-09-24 | 中国科学院大连化学物理研究所 | Monolith catalyst for benzene hydrogenation to cyclohexene and preparation method thereof |
| CN101497040A (en) * | 2008-02-03 | 2009-08-05 | 中国科学院大连化学物理研究所 | Integral catalyst for producing hydrogen dioxide solution as well as preparation and application thereof |
| CN102463125A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin oxychlorination catalyst, preparation method thereof and method for preparing dichloroethane |
| CN105392561A (en) * | 2013-07-17 | 2016-03-09 | 东曹株式会社 | Heterogeneous catalyst and catalyst system for manufacturing 1,2-dichloroethane |
| CN104368336A (en) * | 2013-08-14 | 2015-02-25 | 中国科学院大连化学物理研究所 | Monolithic catalyst for hydrogen peroxide production through pentylanthraquinone process and preparation method thereof |
| CN106732499A (en) * | 2016-12-12 | 2017-05-31 | 北京三聚环保新材料股份有限公司 | A kind of preparation method of the aluminum oxide film layer carrier of monoblock type methyl hydride combustion catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 穆柏春 等: "《陶瓷材料的强韧化》", 31 July 2002, 冶金工业出版社 * |
| 罗民华 编著: "《多孔陶瓷实用技术》", 31 March 2006, 中国建材工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433102A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst with olefin oxychlorination function and preparation method and application thereof |
| CN114433102B (en) * | 2020-11-02 | 2023-10-10 | 中国石油化工股份有限公司 | Catalyst with olefin oxychlorination function, and preparation method and application thereof |
| CN116947473A (en) * | 2023-06-15 | 2023-10-27 | 国能无锡环保科技有限公司 | Method for improving wear resistance of denitration catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6615670B2 (en) | Catalyst and method for chlorine production by gas phase oxidation | |
| US3933883A (en) | Methanation catalyst and process of use | |
| WO1997046317A1 (en) | Epoxidation catalyst and process | |
| CN109110808A (en) | A kind of zirconium colloidal sol and its preparation method and application | |
| WO2017128946A1 (en) | Highly-dispersed particulate catalyst for use in hydrogen peroxide synthesis, preparation method therefor and application thereof | |
| KR20090009896A (en) | Method for producing chlorine by gas phase oxidation | |
| KR20090020635A (en) | Method for producing chlorine by gas phase oxidation | |
| WO2002018043A1 (en) | Attrition resistant bulk iron catalysts and processes for preparing and using same | |
| CN107486195B (en) | Preparation method of low-carbon alkane dehydrogenation catalyst | |
| CN107486197B (en) | Preparation method of low-carbon alkane dehydrogenation microsphere catalyst | |
| CN109745989A (en) | oxychlorination catalyst and its preparation method and application | |
| JP2013230471A (en) | Method of decomposing n2o using catalyst based on cerium lanthanum oxide | |
| CN109745990A (en) | oxychlorination catalyst and its preparation method and application | |
| JP5015057B2 (en) | Catalyst for synthesis of chlorine and method for producing the same, and method for synthesizing chlorine using the catalyst | |
| CN103635256B (en) | The method of the preparation Fischer-Tropsch catalyst containing cobalt | |
| US7256220B2 (en) | Hydrogenation catalyst with improved textural properties | |
| US2917365A (en) | Production of catalyst supports | |
| KR101767899B1 (en) | Method for manufacturing zinc-doped alumina dehydrogenation catalyst | |
| CN114917895A (en) | Preparation method of rare earth denitration catalyst | |
| CN108906116B (en) | Catalyst for synthesizing 2-methyl triethylene diamine and preparation method and application thereof | |
| CN114433099A (en) | Catalyst suitable for ethylene oxychlorination reaction and preparation method and application thereof | |
| JPS6283315A (en) | Production of gamma-alumina having superior heat stability | |
| CN112675827A (en) | Alumina carrier and ethylene oxychlorination catalyst prepared from same | |
| US2657184A (en) | Alumina gel-containing catalysts | |
| CN114433102B (en) | Catalyst with olefin oxychlorination function, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190514 |
|
| RJ01 | Rejection of invention patent application after publication |