CN104437565A - Method for preparing chloroethylene by reaction of chloroform and acetylene, and catalyst used in method - Google Patents
Method for preparing chloroethylene by reaction of chloroform and acetylene, and catalyst used in method Download PDFInfo
- Publication number
- CN104437565A CN104437565A CN201410607592.3A CN201410607592A CN104437565A CN 104437565 A CN104437565 A CN 104437565A CN 201410607592 A CN201410607592 A CN 201410607592A CN 104437565 A CN104437565 A CN 104437565A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acetylene
- chloroform
- vinyl chloride
- cucl
- 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method for preparing chloroethylene by reaction of chloroform and acetylene, and a catalyst used in the method. In the method, the acetylene and the chloroform are taken as raw materials, and the chloroethylene and a byproduct-tetrachloroethylene are further generated in the presence of the non-toxic, harmless and green catalyst. The catalyst takes two or more of FeCl3, AlCl3, CuCl2, CuCl and TiCl4 as active components and takes activated carbon as a carrier, and the non-toxic and harmless load type acetylene hydrochlorination catalyst can be prepared by adopting an impregnation method. The acetylene hydrochlorination process comprises the steps of mixing the acetylene and the chloroform to obtain a mixture, then filling the mixture into a fixed bed reactor filled with the activated carbon catalyst, enabling the acetylene to be hydrochlorinated in the presence of the catalyst to generate the chloroethylene, and carrying out dehydrochlorination on the chloroform to generate the tetrachloroethylene. After the method is used for preparing the chloroethylene, a mercury catalyst or a barium catalyst used for preparing the chloroethylene by acetylene hydrochlorination at present can be avoided, so that the non-polluting production of the chloroethylene can be realized in deed.
Description
Technical field
The invention belongs to chemical field, particularly a kind of take acetylene as carbon source, chloroform is that chlorine source green catalysis produces the method for vinyl chloride.
Background technology
Vinyl chloride is a kind of basic industrial chemicals, and its polymer (PVC) is one of five large general synthetic resins, and have a very wide range of applications field.Along with the increase gradually of vinyl chloride demand, the technology that exploitation vinyl chloride is produced has great importance.At present, global PVC output is more than 5,000 ten thousand t/a, and only the production capacity of Chinese polyvinyl chloride is more than 2,000 ten thousand t/a.Due to resource reason, China's ethylene process technique utilization of capacity is obviously not enough, and its production capacity is only about 25% of aggregated capacity, and the production capacity close to 75% derives from carbide acetylene method technique.Adopt carbide acetylene method to produce vinyl chloride and all adopt hypertoxic mercuric chleride catalyst, cause the pollution of environment and and then harm formed to health.Due to mercury highly volatile, it to be prevented in process of production to be brought in product product quality is impacted, and take the process of catalyst and be also a great difficult problem to the pollution at water source.Therefore, nontoxic green catalysis production process for vinyl chloride is developed extremely urgent.
Current industrial vinyl chloride production method mainly contains ethylene process, ethane oxychlorination method and acetylene method three kinds.Acetylene method technique synthesizing chloroethylene realizes industrialized technology path the earliest.The thirties in 20th century, Germany scientist makes catalyst with mercury chloride, and acetylene and hydrogen chloride are reaction raw materials synthesizing chloroethylene, and finally achieve suitability for industrialized production.What this technology was walked is a typical Coal Chemical Industry Route, first utilize coke and quick lime reaction to produce calcium carbide, then with the calcium carbide generated for raw material and water react obtained acetylene, last acetylene and hydrogen chloride is that catalyst addition obtains vinyl chloride with mercury chloride.This technical matters is simple, it is little to invest, and technology maturation, is applicable to China's development and application, and problem is the mercury pollution adopting acetylene method to produce vinyl chloride must fundamentally to solve.Therefore, the non-mercury catalyst that developing green produces process for vinyl chloride and exploitation asepsis environment-protecting becomes pendulum problem demanding prompt solution in face of whole vinyl chloride industry, is foundation stone and the core of the innovation of acetylene method synthesizing polyvinyl chloride resin technology and sustainable development.
Large quantifier elimination is had both at home and abroad about the acetylene hydrochlorination reaction exploitation of non-mercury catalyst and the exploitation of vinyl chloride green production process.After the nineties, external most of developed country eliminates carbide acetylene method substantially, uses ethylene process instead, and external research report mainly concentrated on before the nineties.In recent years, due to environmental requirement increasingly stringent, the domestic research in this field enlivens gradually.Nineteen sixty-eight Smith etc. (J.Catal., 1968,11 (2): 113 ~ 130) make catalyst activity component with metal chloride, SiO
2make carrier, prepare the catalyst of multiple acetylene gas solid phase hydrogen chlorination reaction, 181 by infusion process
0c, normal pressure, C
2h
2under the condition of/HCl=l:1.3, find that the hydrochlorinate activity of metal chloride has following order: Hg
2+> Bi
3+> Ni
2+> Zn
2+> Cd
2+> Cu
2+> Mn
2+> Ca
2+.1975 Shinoda (Chem. Lett., 1975,4 (3): 219 ~ 22) at 200 DEG C, C
2h
2/ HCl=l:1.3, air speed 150h
-1under, the activity of 20 various metals chlorides/activated-carbon catalyst catalyzing acetylene hydrochlorination is studied, finds that the activity order of different metal ion is: Pd
2+> Hg
2+> Cu
2+> Cu
+> Ag
+.The rugged filial piety hero of rock (JP, clear 51-101905,1976.9.8) iodide exist under, with HAuC1
44H
2o is active precursor, take activated carbon as catalyst carrier, temperature 120 ~ 140 DEG C, and HCl/C
2h
2react under the condition of=1.1, conversion of alkyne 95%, selectively reach 99.5%, within 120 hours, catalyst activity is unchanged, generates in course of reaction without acetylene polymer.United States Patent (USP) (US 5233108,1993.8.3) is reported, take PdCl as catalyst, Shellsol K and Pramene 81-R is mixed solvent, is made into the catalyst system and catalyzing that fusing point is about 25 DEG C, reaction temperature 150 DEG C, and pressure 1.5bar, HCI/C
2h
2be react under the condition of 1.17, vinyl chloride space-time yield reaches 122gh
-1l
-1, the selective of reaction reaches about 90%.As employing PtCI
2make catalyst, under similarity condition, vinyl chloride space-time yield reaches 270gh
-1l
-1, the selective of reaction is 100%.Within 2008, people such as Sichuan University Jiang Wen big grade discloses patent of invention (CN 10124945lA, 2008.8.2), take active carbon as carrier, with precious metal chloride (any one in palladium bichloride, platinum chloride, chlorauride or radium chloride) and base metal chloride (in stannous chloride, cerium chloride and bismuth chloride at least one) for active component, adopt infusion process to prepare the non-mercury catalyst of acetylene hydrochlorination reaction, in continuous-flow fixed bed reaction, react " reaction temperature 110 ~ 160
0c, HCl/C
2h
2=1.05 ~ 1.25, air speed 500 ~ l000 h
-1, conversion of alkyne 95 ~ 98%, vinyl chloride is selective is greater than 99%.Owing to will keep the stable of catalyst activity, need the state of oxidation in the activated centre of managing rugged catalyst, the stability of non-mercury catalyst becomes and is difficult to industrialized main cause.In addition, compared with current mercury catalyst, non-mercury catalyst many employings noble metal is active component, and costly, Cost Problems is also the industrialized key factor of restriction non-mercury catalyst to noble metal catalyst price general charged.Therefore, need manage to develop new vinyl chloride production technology, avoid the use of mercury catalyst.
The exploitation of producing vinyl chloride new technology has been reported.The people such as the Jiang Biao of Zhongke Yigong (Xiamen) Chemical Technology Co., Ltd. (CN201010149210.9) report with lanthanum chloride or barium chloride/active carbon for catalyst, and take ammonium chloride as chlorine source, acetylene is carbon source, in reaction temperature 300 ~ 360
0under C condition, ammonium chloride decomposes and prepares vinyl chloride.Equally, the people such as Jiang Biao (CN 201010149180.1) there was reported with barium chloride/active carbon for catalyst, and dichloroethanes is chlorine source, and acetylene is carbon source, in reaction temperature 250 ~ 320
0preparing chloroethylene by catalytic reforming under C, pressure 0.1 ~ 2MPa condition.These two kinds of methods adopt barium chloride catalyst, although stopped the murder by poisoning of mercury catalyst in vinyl chloride industry, have introduced the pollution of barium chloride.
Summary of the invention
The object of this invention is to provide the catalyst that a kind of chloroform and acetylene reaction produce vinyl chloride, to solve in prior art toxic, the problem polluted of producing and existing in vinyl chloride.
For achieving the above object, the present invention is by the following technical solutions:
Chloroform and acetylene reaction produce a catalyst for vinyl chloride, and this catalyst is with FeCl
3, AlCl
3, CuCl
2, CuCl and TiCl
4in two or more be active component, take active carbon as carrier.
In catalyst, the mass content 3 ~ 28% of active component, the mass content 72 ~ 97% of active carbon, wherein, FeCl
3, AlCl
3, CuCl
2, CuCl and TiCl
4mass content be respectively: 0 ~ 3%, 0 ~ 6%, 0 ~ 6%, 0 ~ 8% and 0 ~ 5%.
Another object of the present invention is to provide the preparation method of above-mentioned catalyst, and its technical scheme is as follows:
Above-mentioned chloroform and acetylene reaction produce a preparation method for the catalyst of vinyl chloride, and catalyst is with FeCl
3, AlCl
3, CuCl
2, CuCl and TiCl
4in two or more be active component, take active carbon as carrier, through dipping, dry, roasting under nitrogen protection, prepare described catalyst.
Preferably, the bake out temperature of catalyst is 100 ~ 200 DEG C.
Preferably, catalyst sintering temperature is under nitrogen protection 300 ~ 500 DEG C.
Another object of the present invention is to provide a kind of method of chloroform and acetylene reaction production vinyl chloride, and its technical scheme is as follows:
A method for chloroform and acetylene reaction production vinyl chloride, under the existence of above-mentioned catalyst, take acetylene as carbon source, chloroform is chlorine source, and a step produces vinyl chloride and tetrachloro-ethylene.
Concrete steps are: take acetylene as carbon source, chloroform is chlorine source, and pass into after acetylene and chloroform gas mixing the fixed bed reactors that activated-carbon catalyst is housed, under the effect of catalyst, acetylene is chlorinated, and generates vinyl chloride, simultaneously by-product tetrachloro-ethylene; Product is after normal temperature condensation, gas-liquid separation, and gas phase obtains vinyl chloride, and liquid phase obtains tetrachloro-ethylene.
Preferably, the mol ratio of acetylene and chloroform gas mixing is 1:1 ~ 1.2.
Preferably, the temperature of acetylene and the reaction of chloroform gaseous mixture is 150 ~ 250 DEG C.
Preferably, the pressure of acetylene and the reaction of chloroform gaseous mixture is 0.1 ~ 1MPa.
The invention has the beneficial effects as follows: method of the present invention generates mercury catalyst or the titanate catalyst that the vinyl chloride acetylene hydrochlorination avoided in existing production produces vinyl chloride, truly achieves the hamlessizing technology of vinyl chloride.In the present invention, conversion of alkyne is between 50% ~ 85%, the selective >95% of vinyl chloride, the selective >98% of trichloro-ethylene.Produce vinyl chloride according to above-mentioned steps, technique is simple, nontoxic, and the green that really can realize vinyl chloride is produced.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described.
embodiment 1
By 1 kg FeCl
36H
2o and 0.6 kg AlCl
36H
2o adds in 12 kg water, and stirring and dissolving obtains the solution that metal salt concentrations is 0.52 mol/L, add active carbon 10 kg, flood 10 hours under room temperature, filter, 110 DEG C dry 10 hours, 400 DEG C roastings 8 hours, obtaining metalline is 8%(mass content) acetylene hydrochlorination catalyst.By acetylene and the mixing of tetrachloroethanes gas, 200 DEG C, pass into fix bed catalyst reactor reaction under 0.1MPa condition, the mol ratio of acetylene and tetrachloroethanes gas and vapor permeation is 1:1, and reaction gas air speed is 200 h
-1, conversion of alkyne is 54%, and vinyl chloride is selective is 97%, and trichloro-ethylene is selective is 98%.
embodiment 2
By 1.5 kg FeCl
36H
2o, 0.8 kg AlCl
36H
2o and 0.5 kg TiCl
4add in 12 kg water, stirring and dissolving, obtain the solution that metal salt concentrations is 0.82 mol/L, add active carbon 10 kg, flood 10 hours under room temperature, filter, 110 DEG C dry 10 hours, 450 DEG C roastings 8 hours, obtaining metalline is 14%(mass content) acetylene hydrochlorination catalyst.By acetylene and the mixing of tetrachloroethanes gas, 220 DEG C, pass into fix bed catalyst reactor reaction under 0.1MPa condition, the mol ratio of acetylene and tetrachloroethanes gas and vapor permeation is 1:1.05, and reaction gas air speed is 500 h
-1, conversion of alkyne is 85%, and vinyl chloride is selective is 96%, and trichloro-ethylene is selective is 99%.
embodiment 3
By 1.5 kg FeCl
36H
2o, 0.8 kg AlCl
36H
2o, 0.8 kg CaCl
22H
2o, 0.5 kg SnCl
22H
2o and 0.3 kg TiCl
4add in 10 kg water, stirring and dissolving, obtain the solution that metal salt concentrations is 1.8 mol/L, add active carbon 10 kg, flood 10 hours under room temperature, filter, 110 DEG C dry 10 hours, 400 DEG C roastings 8 hours, obtaining metalline is 21%(mass content) acetylene hydrochlorination catalyst.By acetylene and the mixing of tetrachloroethanes gas, 250
0pass into fix bed catalyst reactor reaction under C, 0.5MPa condition, the mol ratio of acetylene and tetrachloroethanes gas and vapor permeation is 1:1.02, and reaction gas air speed is 100 h
-1, conversion of alkyne is 81%, and vinyl chloride is selective is 97%, and trichloro-ethylene is selective is 98%.
embodiment 4
By 1.8 kg FeCl
36H
2o, 1 kg AlCl
36H
2o, 1 kg CaCl
22H
2o and 0.8 kg TiCl
4add in 12 kg water, stirring and dissolving, obtain the solution that metal salt concentrations is 1.3 mol/L, add active carbon 10 kg, flood 10 hours under room temperature, filter, 110 DEG C dry 10 hours, 400 DEG C roastings 8 hours, obtaining metalline is 23%(mass content) acetylene hydrochlorination catalyst.By acetylene and the mixing of tetrachloroethanes gas, 240 DEG C, pass into fix bed catalyst reactor reaction under 0.1MPa condition, the mol ratio of acetylene and tetrachloroethanes gas and vapor permeation is 1:1.01, and reaction gas air speed is 200 h
-1, conversion of alkyne is 76%, and vinyl chloride is selective is 98%, and trichloro-ethylene is selective is 99%.
embodiment 5
By 1.8 kg FeCl
36H
2o, 1 kg AlCl
36H
2o, 0.8 kg CaCl
22H
2o, 0.3 kg SnCl
22H
2o and 0.8 kg TiCl
4add in 10 kg water, stirring and dissolving, obtain the solution that metal salt concentrations is 2.0 mol/L, add active carbon 10 kg, flood 10 hours under room temperature, filtration, 110
0c dries 10 hours, 400 DEG C roastings 8 hours, and obtaining metalline is 25%(mass content) acetylene hydrochlorination catalyst.By acetylene and the mixing of tetrachloroethanes gas, 240 DEG C, pass into fix bed catalyst reactor reaction under 1.5MPa condition, the mol ratio of acetylene and tetrachloroethanes gas and vapor permeation is 1:1.02, and reaction gas air speed is 200 h
-1, conversion of alkyne is 66%, and vinyl chloride is selective is 98%, and trichloro-ethylene is selective is 99%.
embodiment 6
By 1 kg AlCl
36H
2o, 1 kg CaCl
22H
2o, 0.8 kg SnCl
22H
2o and 1 kg TiCl
4add in 15 kg water, stirring and dissolving, obtain the solution that metal salt concentrations is 1.0 mol/L, add active carbon 10 kg, flood 10 hours under room temperature, filter, 110 DEG C dry 10 hours, 500 DEG C roastings 8 hours, obtaining metalline is 18%(mass content) acetylene hydrochlorination catalyst.By acetylene and the mixing of tetrachloroethanes gas, 280 DEG C, pass into fix bed catalyst reactor reaction under 0.2MPa condition, the mol ratio of acetylene and tetrachloroethanes gas and vapor permeation is 1:2, and reaction gas air speed is 300 h
-1, conversion of alkyne is 74%, and vinyl chloride is selective is 97%, and trichloro-ethylene is selective is 98%.
Claims (10)
1. chloroform and acetylene reaction produce a catalyst for vinyl chloride, it is characterized in that: catalyst is with FeCl
3, AlCl
3, CuCl
2, CuCl and TiCl
4in two or more be active component, take active carbon as carrier.
2. chloroform as claimed in claim 1 and acetylene reaction produce the catalyst of vinyl chloride, it is characterized in that: in catalyst, the mass content 3 ~ 28% of active component, the mass content 72 ~ 97% of active carbon, wherein, and FeCl
3, AlCl
3, CuCl
2, CuCl and TiCl
4mass content be respectively: 0 ~ 3%, 0 ~ 6%, 0 ~ 6%, 0 ~ 8% and 0 ~ 5%.
3. the arbitrary described chloroform of claim 1-2 and acetylene reaction produce the preparation method of the catalyst of vinyl chloride, it is characterized in that: catalyst is with FeCl
3, AlCl
3, CuCl
2, CuCl and TiCl
4in two or more be active component, take active carbon as carrier, through dipping, dry, roasting under nitrogen protection, prepare described catalyst.
4. chloroform as claimed in claim 3 and acetylene reaction produce the preparation method of the catalyst of vinyl chloride, it is characterized in that: the bake out temperature of catalyst is 100 ~ 200 DEG C.
5. chloroform as claimed in claim 3 and acetylene reaction produce the preparation method of the catalyst of vinyl chloride, it is characterized in that: catalyst sintering temperature is under nitrogen protection 300 ~ 500 DEG C.
6. chloroform and acetylene reaction produce a method for vinyl chloride, it is characterized in that: under the existence of the arbitrary described catalyst of claim 1-2, and take acetylene as carbon source, chloroform is chlorine source, a step produces vinyl chloride and tetrachloro-ethylene.
7. chloroform as claimed in claim 1 and acetylene reaction produce the method for vinyl chloride, it is characterized in that: take acetylene as carbon source, chloroform is chlorine source, the fixed bed reactors that activated-carbon catalyst is housed are passed into by after acetylene and chloroform gas mixing, under the effect of catalyst, acetylene is chlorinated, generate vinyl chloride, simultaneously by-product tetrachloro-ethylene; Product is after normal temperature condensation, gas-liquid separation, and gas phase obtains vinyl chloride, and liquid phase obtains tetrachloro-ethylene.
8. chloroform as claimed in claims 6 or 7 and acetylene reaction produce the method for vinyl chloride, it is characterized in that: the mol ratio of acetylene and chloroform gas mixing is 1:1 ~ 1.2.
9. chloroform as claimed in claims 6 or 7 and acetylene reaction produce the method for vinyl chloride, it is characterized in that: the temperature of acetylene and the reaction of chloroform gaseous mixture is 150 ~ 250 DEG C.
10. chloroform as claimed in claims 6 or 7 and acetylene reaction produce the method for vinyl chloride, it is characterized in that: the pressure of acetylene and the reaction of chloroform gaseous mixture is 0.1 ~ 1MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410607592.3A CN104437565A (en) | 2014-11-03 | 2014-11-03 | Method for preparing chloroethylene by reaction of chloroform and acetylene, and catalyst used in method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410607592.3A CN104437565A (en) | 2014-11-03 | 2014-11-03 | Method for preparing chloroethylene by reaction of chloroform and acetylene, and catalyst used in method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104437565A true CN104437565A (en) | 2015-03-25 |
Family
ID=52884774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410607592.3A Pending CN104437565A (en) | 2014-11-03 | 2014-11-03 | Method for preparing chloroethylene by reaction of chloroform and acetylene, and catalyst used in method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104437565A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588561A (en) * | 2016-12-05 | 2017-04-26 | 扬州大学 | Method for producing tetrachloroethylene by virtue of coupling dehydrochlorination of chloroform |
| CN106694000A (en) * | 2016-12-30 | 2017-05-24 | 中盐常州化工股份有限公司 | Green catalyst for preparing tetrachlorethylene as well as preparation and use methods of green catalyst |
| CN106810416A (en) * | 2016-12-30 | 2017-06-09 | 常州新东化工发展有限公司 | A kind of method of green catalysis production vinyl chloride and trichloro ethylene |
| CN109317169A (en) * | 2018-11-20 | 2019-02-12 | 湖北随州双星生物科技有限公司 | A kind of graphite oxide support type catalyst without mercury and preparation method for synthesis vinyl chloride thereof |
| CN113582812A (en) * | 2021-08-03 | 2021-11-02 | 厦门中科易工化学科技有限公司 | Method for preparing chloroethylene by liquid phase catalysis |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040062941A1 (en) * | 2000-03-15 | 2004-04-01 | Ulrich Kunz | Porous polymer/carrier solid phase reactants, method for producing same and the use thereof |
| CN102675035A (en) * | 2012-06-11 | 2012-09-19 | 上海中科高等研究院 | Method for preparing vinyl chloride from acetylene and dichloroethane |
| CN102911007A (en) * | 2012-11-09 | 2013-02-06 | 中科易工(厦门)化学科技有限公司 | Mercury-free synthetic method of chloroethylene |
| CN103170371A (en) * | 2011-12-21 | 2013-06-26 | 冯良荣 | Catalyst for preparing chloroethylene by acetylene hydrochlorination |
-
2014
- 2014-11-03 CN CN201410607592.3A patent/CN104437565A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040062941A1 (en) * | 2000-03-15 | 2004-04-01 | Ulrich Kunz | Porous polymer/carrier solid phase reactants, method for producing same and the use thereof |
| CN103170371A (en) * | 2011-12-21 | 2013-06-26 | 冯良荣 | Catalyst for preparing chloroethylene by acetylene hydrochlorination |
| CN102675035A (en) * | 2012-06-11 | 2012-09-19 | 上海中科高等研究院 | Method for preparing vinyl chloride from acetylene and dichloroethane |
| CN102911007A (en) * | 2012-11-09 | 2013-02-06 | 中科易工(厦门)化学科技有限公司 | Mercury-free synthetic method of chloroethylene |
Non-Patent Citations (1)
| Title |
|---|
| 秦永真: ""金属离子键参数标定值与乙炔氢氯化反应催化活性的关系"", 《江苏化工》, no. 2, 2 July 1991 (1991-07-02), pages 36 - 1 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588561A (en) * | 2016-12-05 | 2017-04-26 | 扬州大学 | Method for producing tetrachloroethylene by virtue of coupling dehydrochlorination of chloroform |
| CN106694000A (en) * | 2016-12-30 | 2017-05-24 | 中盐常州化工股份有限公司 | Green catalyst for preparing tetrachlorethylene as well as preparation and use methods of green catalyst |
| CN106810416A (en) * | 2016-12-30 | 2017-06-09 | 常州新东化工发展有限公司 | A kind of method of green catalysis production vinyl chloride and trichloro ethylene |
| CN109317169A (en) * | 2018-11-20 | 2019-02-12 | 湖北随州双星生物科技有限公司 | A kind of graphite oxide support type catalyst without mercury and preparation method for synthesis vinyl chloride thereof |
| CN113582812A (en) * | 2021-08-03 | 2021-11-02 | 厦门中科易工化学科技有限公司 | Method for preparing chloroethylene by liquid phase catalysis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104437564A (en) | Catalyst for environment-friendly catalytic production of chloroethylene and method for producing chloroethylene by using catalyst | |
| CN104437565A (en) | Method for preparing chloroethylene by reaction of chloroform and acetylene, and catalyst used in method | |
| Podkolzin et al. | Methyl chloride production from methane over lanthanum-based catalysts | |
| CN104370690B (en) | A kind of anti-form-1, the synthetic method of 1,1,4,4,4-hexafluoro-2-butylene | |
| CN106492869B (en) | A kind of non-noble metal mercury-free catalyst and its preparation method and application for acetylene hydrochlorination reaction | |
| CN104926592A (en) | Method for producing chloroethylene by homogeneous mercury-free catalysis | |
| CN104525237A (en) | Nitrogen-doped active carbon catalyzer and application thereof in chloroethylene synthesis | |
| CN107442171B (en) | Supported quaternary ammonium salt and metal chloride catalyst and preparation method thereof | |
| CN108993595B (en) | Copper-based catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene and preparation method and application thereof | |
| CN107667086A (en) | The method for preparing vinyl chloride | |
| CN107744836A (en) | A kind of preparation method and applications of load-type ion liquid catalyst | |
| CN105330512A (en) | Method for preparing chloroethylene from acetylene and hydrogen chloride in mercuration-free mode | |
| JPH04501871A (en) | Low temperature catalyst for oxidative coupling method | |
| CN106694000A (en) | Green catalyst for preparing tetrachlorethylene as well as preparation and use methods of green catalyst | |
| CN105727929A (en) | Fluorination catalyst with high specific surface area, preparation method thereof and application | |
| CN102806095B (en) | Multi-component non-mercury accelerant for preparing vinyl chloride through acetylene hydrochlorination and application method of multi-component non-mercury accelerant | |
| CN103846101B (en) | A kind of C-SiC catalyst and Synthesis and applications thereof | |
| CN113582812A (en) | Method for preparing chloroethylene by liquid phase catalysis | |
| CN106810416A (en) | A kind of method of green catalysis production vinyl chloride and trichloro ethylene | |
| US20230081584A1 (en) | Preparation method of 1-chloro-2,3,3-trifluoropropene | |
| US7968755B2 (en) | Process and catalyst for converting alkanes | |
| CN110204425A (en) | A kind of method for transformation of the carbon-halogen bond C-R of photocatalysis polyhalide to hydrocarbon/deuterium key C-H/D | |
| CN110615895B (en) | Covalent triazine polymer and preparation method and application thereof | |
| US3527819A (en) | Oxychlorination process for preparing trichloroethylene and tetrachloroethylene | |
| CN106278805B (en) | A kind of preparation method of vinylidene chloride monomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150325 |
|
| RJ01 | Rejection of invention patent application after publication |