CN106397108A - Application of catalyst used for preparation of vinyl chloride to catalysis of one-step preparation of vinyl chloride from dichloroethane and acetylene - Google Patents
Application of catalyst used for preparation of vinyl chloride to catalysis of one-step preparation of vinyl chloride from dichloroethane and acetylene Download PDFInfo
- Publication number
- CN106397108A CN106397108A CN201510467522.7A CN201510467522A CN106397108A CN 106397108 A CN106397108 A CN 106397108A CN 201510467522 A CN201510467522 A CN 201510467522A CN 106397108 A CN106397108 A CN 106397108A
- Authority
- CN
- China
- Prior art keywords
- chloride
- catalyst
- vinyl chloride
- acetylene
- preparation
- 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.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses application of a catalyst used for preparation of vinyl chloride to catalysis of one-step preparation of vinyl chloride from dichloroethane and acetylene. A preparation method for the catalyst used for preparation of vinyl chloride comprises the following steps: (1) impregnating a catalyst carrier in a quaternary phosphonium salt solution and evaporating the solvent to dryness so as to obtain the quaternary phosphonium salt-loaded carrier; and (2) impregnating the quaternary phosphonium salt-loaded carrier with an aqueous solution of metal chloride by using an equivalent-volume impregnation method and carrying out drying. As the catalyst is used for catalyzing a one-step reaction of dichloroethane with acetylene for preparation of vinyl chloride, reaction temperature is substantially lowered, energy consumption is decreased, coking and carbon formation of a reactor are reduced, and the service life of the catalyst is prolonged. Under the conditions that a reaction temperature is 180 to 250 DEG C, reaction pressure is 0.1 to 1 MPa, a mol ratio of acetylene to dichloroethane is 1: 1 and the space velocity of acetylene is 10 to 360/h, the conversion rate of acetylene is 57 to 99%, the selectivity of produced vinyl chloride is 99.5% or above, and the activity of the catalyst has no obvious change in a reaction having lasted for 180 h.
Description
Technical field
The present invention relates to a kind of purposes of the catalyst preparing vinyl chloride.
Background technology
With the raising of the development of national economy, increasingly raising and the environmental protection consciousness of living standards of the people, PVC (polrvinyl chloride)
Demand increasing.PVC is obtained by VCM (Vinyl Chloride Monomer) polymerization, and the production method of VCM mainly has second
Alkene method technique, ethane method technique and acetylene method technique.Ethylene process prepares PVC as the process route of a technology maturation, alive
The PVC production technology of main flow is always on boundary, especially in the country of developed country and rich in petroleum resources.Ethylene process production technology
With petrochemicals ethylene as raw material, direct chlorination or oxychlorination generate dichloroethanes (EDC), then by high for EDC anneal crack
Solution dehydrochlorination can obtain VCM.This technique is more complicated, and technical requirements and equipment investment are high, but good product quality, with oil
Developed country for main energy sources mainly adopts this technique.The problem of ethylene process technique is mainly：High energy consumption, cracking furnace coking is tight
Weight, needs regular coke cleaning, affects continuity of operation.Ethane method low cost, but also in the laboratory research stage.Acetylene method
Meet the national conditions of rich coal resources in China, but due to using mercuric chleride catalyst, there is serious mercury pollution problem.
It is a kind of method of new synthesis vinyl chloride thereof that dichloroethanes and acetylene one-step method prepare vinyl chloride, and equipment investment is low, and energy consumption is low,
It is a kind of promising method for synthesizing chloroethylene.The maximum difficult point of the method is catalyst activity under low temperature and high-speed at present
Not high.
Jiang Biao of Zhongke Yigong (Xiamen) Chemical Technology Co., Ltd. etc. is special in the Chinese invention of Publication No. CN101817723A
It is proposed that a kind of carried catalyst of barium chloride load is catalyzed the method that dichloroethanes and acetylene one-step method prepare vinyl chloride in profit.
Carrier using barium chloride load makees catalyst, in 0.1MPa, 320 DEG C and 15h-1Dichloroethanes vapor superficial velocities under be catalyzed two
Ethyl chloride and acetylene one-step method prepare vinyl chloride, and conversion of alkyne is 70%.
Jiang Biao of Shanghai Advanced Research Institute, Chinese Academy of Sciences etc., in the Chinese invention patent of Publication No. CN104289246A, carries
Go out the method that the catalyst dichloroethanes of a kind of carrier loaded barium chloride and phosphoric acid and acetylene one-step method prepare vinyl chloride.?
0.1MPa, 250 DEG C and 15h-1Dichloroethanes vapor superficial velocities under catalysis dichloroethanes and acetylene one-step method prepare vinyl chloride, second
Alkynes conversion ratio is 84.5%.
Jiang Biao of Shanghai Advanced Research Institute, Chinese Academy of Sciences etc., in the Chinese invention patent of Publication No. CN102441407A, carries
Go out a kind of nitrating carried catalyst and be catalyzed the method that dichloroethanes and acetylene one-step method prepare vinyl chloride.Using nitrogen-containing compound with
Nitrating carrier is prepared in 400-800 DEG C of calcining, in 0.1MPa, 250 DEG C and 15h after carrier impregnation-1Dichloroethanes steam
Under air speed, catalysis dichloroethanes and acetylene one-step method prepare vinyl chloride, and conversion of alkyne is 65.3%.
However, the activity of these dichloroethanes and acetylene one-step method catalyst of preparing vinyl chloride still has much room for improvement, especially low
Activity under gentle high-speed still has much room for improvement.
Content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, provides the catalyst preparing vinyl chloride in catalysis dichloroethanes and acetylene
One-step method prepares the purposes of vinyl chloride.
Technical solution of the present invention is summarized as follows：
Prepare the purposes that vinyl chloride prepared by the catalyst of vinyl chloride in catalysis dichloroethanes and acetylene one-step method, described prepare vinyl chloride
Catalyst made with following methods：
(1) quaternary salt is dissolved in solvent and is made into quaternary salt solution, then catalyst carrier is immersed in quaternary salt solution, make quaternary salt
Mass ratio with catalyst carrier is 0.5-40:100；It is evaporated molten after constant temperature 2-12h under 30-100 DEG C of water-bath at 100-150 DEG C
Agent obtains the carrier having loaded quaternary salt；
(2) adopting equi-volume impregnating that the carrier having loaded quaternary salt that step (1) obtains is dipped in mass concentration is 0.05%-5%'s
In metal chloride aqueous solution, 60 DEG C of evaporating water, 100-150 DEG C of drying.
Described quaternary salt is THPC, tetramethyl phosphonium chloride, tetrabutylphosphonium chloride, tetraphenylphosphonium chloride, methyl three
Tetraphenylphosphonium chloride phosphine, ethyltriphenyl phosphonium chloride phosphine, (tributyl) n-tetradecane base phosphonium chloride, tetrabutyl phosphonium bromide phosphine or tetraphenylphosphonibromide bromide
Phosphine.
Solvent is preferably water, methanol, ethanol, acetone, ethylene glycol, toluene, dimethylbenzene, dichloroethanes or chloroform.
Catalyst carrier is preferably activated carbon, aluminium oxide, silica gel or 5A molecular sieve.
Metal chloride is preferably barium chloride, strontium chloride, calcium chloride, copper chloride or ruthenium trichloride.
Prepare chloroethene alkene reaction with the catalyst dichloroethanes and acetylene one-step method preparing vinyl chloride, reaction temperature can be made big
Big reduction, thus reducing energy consumption, reduces reactor carbon distribution and coking, improves catalyst life；It is 180-250 in reaction temperature
DEG C, the amount ratio of 0.1-1MPa, acetylene and dichloroethanes material be 1:1, acetylene air speed is 10-360h-1Under the conditions of, acetylene turns
Rate is 57-99%, and the selectivity generating vinyl chloride is more than 99.5%, activity no significant change in 180h sustained response.
Specific embodiment
Below by embodiment, the present invention is specifically described, to make those skilled in the art can be better understood from this
Invention.But illustrated embodiment is not intended as the present invention is limited in any way.
Embodiment 1
Blank activated carbon (AC) prepares the test (reference) of chloroethene alkene reaction as catalyst dichloroethanes and acetylene one-step method
Reaction condition is 250 DEG C of reaction temperature, the amount ratio of normal pressure, acetylene and dichloroethanes material is 1:1, acetylene air speed is 36
h-1Under the conditions of, conversion of alkyne is 1%, and the selectivity generating vinyl chloride is more than 99.3%, activity nothing in 180h sustained response
Significant change.
Embodiment 2
Prepare the preparation of the catalyst of vinyl chloride：
4g THPC is dissolved in 40g methanol and is made into THPC solution, then 20 activated carbons are impregnated
To in above-mentioned solution, under 30 DEG C of water-baths, constant temperature dipping 12h, 100 DEG C of solvent evaporated recycling design, must load four hydroxyl first
The activated carbon of base phosphorus chloride；
The activated carbon having loaded THPC is dipped in by the ruthenium trichloride that mass concentration is 0.05% using equi-volume impregnating
In aqueous solution, 60 DEG C of water bath method moisture, then dry to obtain required catalyst in 150 DEG C of baking ovens.
Reaction condition is 250 DEG C of reaction temperature, the amount ratio of normal pressure, acetylene and dichloroethanes material is 1:1, acetylene air speed is
10h-1Under the conditions of, conversion of alkyne is 98%, and the selectivity generating vinyl chloride is more than 99.5%, lives in 180h sustained response
Property no significant change.Compare the blank AC catalyst of embodiment 1, the conversion of alkyne of the catalyst of the present invention improves 97%.
Embodiment 3
Prepare the preparation of the catalyst of vinyl chloride：
8g tetramethyl phosphonium chloride is dissolved in 40g water and is made into tetramethyl phosphonium chloride solution, then 20g aluminium oxide is impregnated into above-mentioned
In solution, under 100 DEG C of water-baths, constant temperature dipping 2h, 150 DEG C of solvent evaporated recycling design, must load tetramethyl phosphonium chloride
Aluminium oxide.
The aluminium oxide having loaded tetramethyl phosphonium chloride is dipped in by the copper chloride solution that mass concentration is 5% using equi-volume impregnating
In, 60 DEG C of water bath method moisture, then dry to obtain required catalyst in 100 DEG C of baking ovens.
Reaction condition is 200 DEG C of reaction temperature, the amount ratio of 0.2MPa, acetylene and dichloroethanes material is 1:1, acetylene air speed
For 360h-1Under the conditions of, conversion of alkyne is 57%, and the selectivity generating vinyl chloride is more than 99.5%, in 180h sustained response
The no significant change of middle activity.Compare the blank AC catalyst of embodiment 1, the conversion of alkyne of the catalyst of the present invention improves
56%.
Embodiment 4
Prepare the preparation of the catalyst of vinyl chloride：
0.1g tetrabutylphosphonium chloride is dissolved in 40g ethanol and is made into tetrabutylphosphonium chloride solution, then 20g silica gel is impregnated into
State in solution, under 70 DEG C of water-baths, constant temperature dipping 5h, 110 DEG C of solvent evaporated recycling design, have loaded tetrabutylphosphonium chloride
Silica gel；
The silica gel having loaded tetrabutylphosphonium chloride is dipped in by the barium chloride solution that mass concentration is 0.5% using equi-volume impregnating
In, 60 DEG C of water bath method moisture, then dry to obtain required catalyst in 120 DEG C of baking ovens.
Reaction condition is 180 DEG C of reaction temperature, the amount ratio of 1MPa, acetylene and dichloroethanes material is 1:1, acetylene air speed is
120h-1, conversion of alkyne is 76%, and the selectivity generating vinyl chloride is more than 99.5%, activity nothing in 180h sustained response
Significant change.Compare the blank AC catalyst of embodiment 1, the conversion of alkyne of the catalyst of the present invention improves 75%.
Embodiment 5
Prepare the preparation of the catalyst of vinyl chloride：
2g tetraphenylphosphonium chloride is dissolved in 40g acetone and is made into tetraphenylphosphonium chloride solution, then 20g5A molecular sieve is impregnated into
In above-mentioned solution, under 60 DEG C of water-baths, constant temperature dipping 8h, 120 DEG C of solvent evaporated recycling design, must load tetraphenylphosphonichloride chloride
The 5A molecular sieve of phosphine.
The 5A molecular sieve having loaded tetraphenylphosphonium chloride is dipped in by the strontium chloride that mass concentration is 0.25% using equi-volume impregnating
In aqueous solution, 60 DEG C of water bath method moisture, then dry to obtain required catalyst in 140 DEG C of baking ovens.
Reaction condition is 250 DEG C of reaction temperature, the amount ratio of normal pressure, acetylene and dichloroethanes material is 1:1, acetylene air speed is
90h-1, conversion of alkyne is 92%, and the selectivity generating vinyl chloride is more than 99.5%, and in 180h sustained response, activity is no bright
Aobvious change.Compare the blank AC catalyst of embodiment 1, the conversion of alkyne of the catalyst of the present invention improves 91%.
Embodiment 6
Prepare the preparation of the catalyst of vinyl chloride：
4g methyl triphenyl phosphonium chloride is dissolved in 40g ethylene glycol and is made into methyl triphenyl phosphonium chloride solution, then 20g is active
Charcoal is impregnated in above-mentioned solution, and under 80 DEG C of water-baths, constant temperature dipping 10h, 150 DEG C of solvent evaporated recycling design, must load first
The activated carbon of base triphenyl phosphine dichloride.
The activated carbon having loaded methyl triphenyl phosphonium chloride is dipped in by the calcium chloride water that mass concentration is 2% using equi-volume impregnating
In solution, 60 DEG C of water bath method moisture, then dry to obtain required catalyst in 130 DEG C of baking ovens.
Reaction condition is 220 DEG C of reaction temperature, the amount ratio of normal pressure, acetylene and dichloroethanes material is 1:1, acetylene air speed is
90h-1, conversion of alkyne is 64%, and the selectivity generating vinyl chloride is more than 99.5%, and in 180h sustained response, activity is no bright
Aobvious change.Compare the blank AC catalyst of embodiment 1, the conversion of alkyne of the catalyst of the present invention improves 63%.
Embodiment 7
Prepare the preparation of the catalyst of vinyl chloride：
4g (tributyl) n-tetradecane base phosphonium chloride is dissolved in 40g toluene and is made into (tributyl) n-tetradecane base phosphonium chloride solution,
Again 20g activated carbon is impregnated in above-mentioned solution, constant temperature dipping 12h under 80 DEG C of water-baths, 130 DEG C of solvent evaporated simultaneously reclaim molten
Agent, obtains the AC of load (tributyl) n-tetradecane base phosphonium chloride.
The activated carbon loading (tributyl) n-tetradecane base phosphonium chloride is dipped in by the chlorine that mass concentration is 4% using equi-volume impregnating
Change in copper liquor, 60 DEG C of water bath method moisture, then dry to obtain required catalyst in 130 DEG C of baking ovens.
Reaction condition is 230 DEG C of reaction temperature, the amount ratio of 0.4MPa, acetylene and dichloroethanes material is 1:1, acetylene air speed
For 60h-1, conversion of alkyne is 60%, and the selectivity generating vinyl chloride is more than 99.5%, activity nothing in 180h sustained response
Significant change.Compare the blank AC catalyst of embodiment 1, the conversion of alkyne of the catalyst of the present invention improves 59%.
Embodiment 8
Prepare the preparation of the catalyst of vinyl chloride：
4g tetrabutyl phosphonium bromide phosphine is dissolved in 40g dichloroethanes and is made into tetrabutyl phosphonium bromide phosphine solution, then 20g activated carbon is impregnated
To in above-mentioned solution, under 40 DEG C of water-baths, constant temperature dipping 9h, 140 DEG C of solvent evaporated recycling design, must load tetrabutyl bromine
Change the activated carbon of phosphine.
The activated carbon having loaded tetrabutyl phosphonium bromide phosphine is dipped in by the ruthenium trichloride water that mass concentration is 0.25% using equi-volume impregnating
In solution, 60 DEG C of water bath method moisture, then dry to obtain required catalyst in 150 DEG C of baking ovens.
Reaction condition is 210 DEG C of reaction temperature, the amount ratio of normal pressure, acetylene and dichloroethanes material is 1:1, acetylene air speed is
30h-1, conversion of alkyne is 99%, and the selectivity generating vinyl chloride is more than 99.5%, and in 180h sustained response, activity is no bright
Aobvious change.Compare the blank AC catalyst of embodiment 1, the conversion of alkyne of the catalyst of the present invention improves 98%.
Embodiment 9
Prepare the preparation of the catalyst of vinyl chloride：
3g tetraphenylphosphonibromide bromide is dissolved in 40g dimethylbenzene and is made into tetraphenylphosphonibromide bromide solution, then 20g activated carbon is impregnated into
In above-mentioned solution, under 60 DEG C of water-baths, constant temperature dipping 8h, 150 DEG C of solvent evaporated recycling design, must load tetraphenyl bromine
Change the activated carbon of phosphine.
The activated carbon having loaded tetraphenylphosphonibromide bromide is dipped in by the ruthenium trichloride water that mass concentration is 0.2% using equi-volume impregnating
In solution, 60 DEG C of water bath method moisture, then dry to obtain required catalyst in 150 DEG C of baking ovens.
Reaction condition is 190 DEG C of reaction temperature, the amount ratio of normal pressure, acetylene and dichloroethanes material is 1:1, acetylene air speed is
36h-1, conversion of alkyne is 59%, and the selectivity generating vinyl chloride is more than 99.5%, and in 180h sustained response, activity is no bright
Aobvious change.Compare the blank AC catalyst of embodiment 1, the conversion of alkyne of the catalyst of the present invention improves 58%.
Embodiment 10
Prepare the preparation of the catalyst of vinyl chloride：
2g ethyltriphenyl phosphonium chloride phosphine is dissolved in 40g chloroform and is made into ethyltriphenyl phosphonium chloride phosphine solution, then 20g is lived
Property charcoal be impregnated in above-mentioned solution, constant temperature dipping 7h under 50 DEG C of water-baths, 150 DEG C of solvent evaporated recycling design, obtain load
The activated carbon AC of ethyltriphenyl phosphonium chloride phosphine.
The activated carbon having loaded ethyltriphenyl phosphonium chloride phosphine is dipped in by the barium chloride that mass concentration is 0.5% using equi-volume impregnating
In aqueous solution, 60 DEG C of water bath method moisture, then dry to obtain required catalyst in 130 DEG C of baking ovens.
Reaction condition is 250 DEG C of reaction temperature, the amount ratio of normal pressure, acetylene and dichloroethanes material is 1:1, acetylene air speed is
180h-1, conversion of alkyne is 69%, and the selectivity generating vinyl chloride is more than 99.5%, activity nothing in 180h sustained response
Significant change.Compare the blank AC catalyst of embodiment 1, the conversion of alkyne of the catalyst of the present invention improves 68%.
Claims (5)
1. the purposes of vinyl chloride prepared by the catalyst preparing vinyl chloride in catalysis dichloroethanes and acetylene one-step method, it is characterized in that described preparation
The catalyst of vinyl chloride is made with following methods：
(1) quaternary salt is dissolved in solvent and is made into quaternary salt solution, then catalyst carrier is immersed in quaternary salt solution, make quaternary salt
Mass ratio with catalyst carrier is 0.5-40:100；It is evaporated molten after constant temperature 2-12h under 30-100 DEG C of water-bath at 100-150 DEG C
Agent obtains the carrier having loaded quaternary salt；
(2) adopting equi-volume impregnating that the carrier having loaded quaternary salt that step (1) obtains is dipped in mass concentration is 0.05%-5%'s
In metal chloride aqueous solution, 60 DEG C of water bath method moisture, 100-150 DEG C of drying.
2. purposes according to claim 1, is characterized in that described quaternary salt is THPC, tetramethyl phosphonium chloride, four
Butyl phosphonium chloride, tetraphenylphosphonium chloride, methyl triphenyl phosphonium chloride, ethyltriphenyl phosphonium chloride phosphine, (tributyl) n-tetradecane base
Phosphonium chloride, tetrabutyl phosphonium bromide phosphine or tetraphenylphosphonibromide bromide.
3. purposes according to claim 1, it is characterized in that described solvent be water, methanol, ethanol, acetone, ethylene glycol, toluene,
Dimethylbenzene, dichloroethanes or chloroform.
4. purposes according to claim 1, is characterized in that described catalyst carrier is that activated carbon, aluminium oxide, silica gel or 5A divide
Son sieve.
5. purposes according to claim 1, is characterized in that described metal chloride is barium chloride, strontium chloride, calcium chloride, chlorination
Copper or ruthenium trichloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510467522.7A CN106397108B (en) | 2015-07-31 | 2015-07-31 | The catalyst for preparing vinyl chloride prepares the purposes of vinyl chloride in catalysis dichloroethanes and acetylene one-step method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510467522.7A CN106397108B (en) | 2015-07-31 | 2015-07-31 | The catalyst for preparing vinyl chloride prepares the purposes of vinyl chloride in catalysis dichloroethanes and acetylene one-step method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106397108A true CN106397108A (en) | 2017-02-15 |
| CN106397108B CN106397108B (en) | 2018-07-10 |
Family
ID=58007828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510467522.7A Active CN106397108B (en) | 2015-07-31 | 2015-07-31 | The catalyst for preparing vinyl chloride prepares the purposes of vinyl chloride in catalysis dichloroethanes and acetylene one-step method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106397108B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008465A (en) * | 2017-03-31 | 2017-08-04 | 清华大学 | A kind of acetylene hydrochlorination reaction copper-based catalysts with high-activity stable |
| WO2018049820A1 (en) * | 2016-09-18 | 2018-03-22 | 天津大学 | Use of catalyst supporting quaternary phosphonium salt and metal chloride for acetylene hydrochlorination |
| CN111151299A (en) * | 2019-09-29 | 2020-05-15 | 浙江工业大学 | Copper alkoxide complex catalyst, preparation method thereof and application thereof in acetylene hydrochlorination |
| CN112844460A (en) * | 2019-11-27 | 2021-05-28 | 中国科学院大连化学物理研究所 | Catalyst for preparing chloroethylene by acetylene and dichloroethane coupling reaction and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102441407A (en) * | 2011-10-26 | 2012-05-09 | 上海中科高等研究院 | Catalyst used for vinyl chloride preparation, its preparation method and application |
| WO2012084642A1 (en) * | 2010-12-22 | 2012-06-28 | Solvay Sa | Manufacture of vinyl chloride by hydrochlorination of acetylene in the presence of a catalytic system consisting of at least one ionic liquid |
| CN103269796A (en) * | 2010-12-22 | 2013-08-28 | 索维公司 | Catalytic system and its use for the manufacture of vinyl chloride by hydrochlorination of acetylene |
| CN103391911A (en) * | 2011-02-24 | 2013-11-13 | 索维公司 | Process for the hydrohalogenation of an alkyne and for the manufacture of vinyl chloride by hydrochlorination of acetylene |
| CN104109076A (en) * | 2014-06-30 | 2014-10-22 | 浙江大学 | Method for preparing vinyl chloride by hydrochlorinating acetylene through using quaternary phosphonium long-chain ionic liquid as medium |
| CN104549522A (en) * | 2013-10-16 | 2015-04-29 | 阳永荣 | Mercury-free catalyst for preparation of VCM (vinyl chloride monomer) through acetylene hydrochlorination and using method |
-
2015
- 2015-07-31 CN CN201510467522.7A patent/CN106397108B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012084642A1 (en) * | 2010-12-22 | 2012-06-28 | Solvay Sa | Manufacture of vinyl chloride by hydrochlorination of acetylene in the presence of a catalytic system consisting of at least one ionic liquid |
| CN103269796A (en) * | 2010-12-22 | 2013-08-28 | 索维公司 | Catalytic system and its use for the manufacture of vinyl chloride by hydrochlorination of acetylene |
| CN103391911A (en) * | 2011-02-24 | 2013-11-13 | 索维公司 | Process for the hydrohalogenation of an alkyne and for the manufacture of vinyl chloride by hydrochlorination of acetylene |
| CN102441407A (en) * | 2011-10-26 | 2012-05-09 | 上海中科高等研究院 | Catalyst used for vinyl chloride preparation, its preparation method and application |
| CN104549522A (en) * | 2013-10-16 | 2015-04-29 | 阳永荣 | Mercury-free catalyst for preparation of VCM (vinyl chloride monomer) through acetylene hydrochlorination and using method |
| CN104109076A (en) * | 2014-06-30 | 2014-10-22 | 浙江大学 | Method for preparing vinyl chloride by hydrochlorinating acetylene through using quaternary phosphonium long-chain ionic liquid as medium |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018049820A1 (en) * | 2016-09-18 | 2018-03-22 | 天津大学 | Use of catalyst supporting quaternary phosphonium salt and metal chloride for acetylene hydrochlorination |
| CN107008465A (en) * | 2017-03-31 | 2017-08-04 | 清华大学 | A kind of acetylene hydrochlorination reaction copper-based catalysts with high-activity stable |
| CN111151299A (en) * | 2019-09-29 | 2020-05-15 | 浙江工业大学 | Copper alkoxide complex catalyst, preparation method thereof and application thereof in acetylene hydrochlorination |
| CN111151299B (en) * | 2019-09-29 | 2020-10-09 | 浙江工业大学 | Copper alkoxide complex catalyst, preparation method thereof and application thereof in acetylene hydrochlorination |
| CN112844460A (en) * | 2019-11-27 | 2021-05-28 | 中国科学院大连化学物理研究所 | Catalyst for preparing chloroethylene by acetylene and dichloroethane coupling reaction and application thereof |
| CN112844460B (en) * | 2019-11-27 | 2022-06-03 | 中国科学院大连化学物理研究所 | Catalyst for preparing chloroethylene by acetylene and dichloroethane coupling reaction and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106397108B (en) | 2018-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106391125B (en) | The catalyst and Preparation method and use of vinyl chloride are prepared for dichloroethanes low temperature antichloration hydrogen | |
| CN106391078A (en) | Catalyst used for one-step preparation of vinyl chloride from dichloroethane and acetylene, and preparation method and application thereof | |
| CN106397108B (en) | The catalyst for preparing vinyl chloride prepares the purposes of vinyl chloride in catalysis dichloroethanes and acetylene one-step method | |
| CN107837824A (en) | Purposes of the catalyst of load quaternary alkylphosphonium salt and metal chloride in acetylene hydrochlorination | |
| CN105251486A (en) | Supported platinum group catalyst applied to propane dehydrogenation propylene preparation and preparation method of supported platinum group catalyst | |
| CN104588011B (en) | Alkane dehydrogenation catalyst and preparation method thereof | |
| CN101890360A (en) | Method for preparing novel catalyst used for hydrochlorination of acetylene | |
| CN105983428A (en) | Catalyst used in low-temperature removal of hydrogen chloride from dichloroethane for preparation of vinyl chloride, and preparation method and application thereof | |
| CN109513449B (en) | Method for preparing solid super acid from metal organic framework material UiO-66, product and application thereof | |
| CN105541610A (en) | Method for synthesizing methyl propionate with carbon dioxide and ethylene | |
| CN105396582B (en) | A kind of catalyst for preparing propylene with propane dehydrogenation and its preparation method and application | |
| CN102151573A (en) | Preparation method of low-mercury catalyst for preparing vinyl chloride | |
| CN104289219B (en) | Preparation method for low carbon alkane dehydrogenation catalyst | |
| CN107537476A (en) | Dehydrogenation, preparation method and its usage | |
| CN102766018A (en) | Chloroethylene preparation method by catalytic cracking by barium chloride catalyst | |
| CN104941638B (en) | A kind of dehydrogenation and its preparation and application | |
| CN105435768B (en) | The process of alcoholysis of urea for synthesizing propylene carbonate and the preparation method of catalyst | |
| CN113941344A (en) | Phosphorus modified activated carbon and low-mercury catalyst prepared by taking phosphorus modified activated carbon as carrier | |
| CN112871207B (en) | Supported non-metal catalyst and preparation method and application thereof | |
| CN102151579A (en) | Copper phosphide catalyst for synthesizing chloroethylene and preparation method thereof | |
| CN111715258A (en) | Nitrogen-doped carbon-based catalyst and application thereof in preparation of vinyl chloride by catalyzing hydrochlorination of acetylene | |
| DK2448671T3 (en) | Multi metallic catalyst with a strong metal interaction | |
| CN1384176A (en) | Reforming catalyst containing molecular sieve | |
| CN1261214C (en) | Bifunctional multi-metal reforming catalyst and its preparing method | |
| CN115608359A (en) | Copper catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 300350 Haijing garden, Haihe Education Park, Jinnan, Tianjin, 135, Tianjin University. Patentee after: Tianjin University Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Patentee before: Tianjin University |