CN109876864B - Ultralow-content noble metal composite catalyst for acetylene hydrochlorination and preparation method thereof - Google Patents
Ultralow-content noble metal composite catalyst for acetylene hydrochlorination and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ultra-low content noble metal composite catalyst for acetylene hydrochlorination and a preparation method thereof, the catalyst is prepared by loading a noble metal-amino acid complex and a cocatalyst component on acid-treated active carbon, wherein the amino acid is cysteine, glutamine, asparagine and the like, and the cocatalyst component is copper chloride, cobalt chloride, cerium chloride, bismuth chloride, cesium chloride and the like; the mass contents of the noble metal and the cocatalyst component in the catalyst are respectively 0.05-0.25% and 0.06-0.90%. The catalyst has excellent catalytic activity, selectivity and long service life in acetylene hydrochlorination, and can keep the acetylene conversion rate over 98.5 percent and the chloroethylene selectivity over 99 percent in long-time operation.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to an ultralow-content noble metal composite catalyst for acetylene hydrochlorination and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is the second most common synthetic resin in the world, and in recent years, the process for preparing vinyl chloride monomer by using a calcium carbide method (an acetylene method) is rapidly developed in China and becomes the mainstream of the PVC industry. However, the preparation of vinyl chloride by the acetylene method basically adopts mercuric chloride as an active component of a catalyst, the catalyst has high activity and selectivity and low price, but the catalyst has the biggest problem of poor thermal stability, and the mercuric chloride with high toxicity is continuously volatilized in the use process, so that the catalyst has low activity and causes serious pollution to the environment.
In the long term, the elimination of the mercuric chloride catalyst is imperative, so the development of the environment-friendly and nontoxic mercury-free catalyst is an urgent problem to be solved in the whole PVC industry, and the extensive attention of domestic and foreign scholars is also aroused. The noble metal catalyst is considered to be the mercury-free catalyst which is most expected to replace the mercuric chloride catalyst to be applied to the acetylene hydrochlorination reaction, but the price of the noble metal is far higher than that of the mercuric chloride in terms of cost, which is one of the main factors hindering the industrial application of the catalyst.
Noble metals as active components can show good catalytic activity in acetylene hydrochlorination, because the logarithm value of the catalytic activity of noble metals and the standard electrode potential value of the oxidation state of noble metals are in a linear relationship. In summary, the noble metal catalyst used for preparing vinyl chloride by hydrochlorinating acetylene has good selectivity and activity but poor stability, and the development of the acetylene hydrochlorinating noble metal catalyst for industrial application to replace the mercury-containing catalyst which is mature and applied at present also faces many technical problems to be solved. The key technical difficulty is how to reduce the cost of the catalyst and solve the problem of rapid inactivation of the catalyst in the reaction process.
Disclosure of Invention
The present invention aims at overcoming the shortcomings of the prior art and providing an ultra-low content noble metal composite catalyst with excellent catalytic activity, selectivity and long service life for acetylene hydrochlorination.
Aiming at the purposes, the ultralow-content precious metal composite catalyst adopted by the invention takes acid-treated activated carbon as a carrier, and carries a precious metal-amino acid complex and a cocatalyst component, wherein the amino acid is any one of cysteine, glutamine and asparagine or any one of derivatives thereof, and the cocatalyst component is any one or more than two of copper chloride, cobalt chloride, cerium chloride, bismuth chloride and cesium chloride; the mass content of the noble metal in the catalyst is 0.05-0.25%, and the mass content of the cocatalyst component is 0.06-0.90%.
In the catalyst, the mass content of the noble metal is preferably 0.1-0.2%, and the mass content of the cocatalyst component is preferably 0.25-0.65%.
In the catalyst, the noble metal is any one of gold, ruthenium and palladium, and gold is preferred.
The cocatalyst component is any one or more than two of copper chloride, cobalt chloride and cerium chloride.
The activated carbon is any one of wood activated carbon, coconut shell activated carbon and coal activated carbon, and is in any one of a columnar shape, a sheet shape and a spherical shape.
The noble metal composite catalyst is prepared by the following method:
1. washing activated carbon with tap water to remove surface impurity ash, then adding the activated carbon into an acid aqueous solution with the mass fraction of 5% -20%, heating and boiling for 1h, cooling, repeatedly soaking and washing with deionized water until the pH value of a washing liquid is more than 4, and drying to obtain the acid-treated activated carbon.
2. And dropwise adding an amino acid aqueous solution into the aqueous solution of the noble metal soluble salt according to the molar ratio of the noble metal soluble salt to the amino acid of 1: 2-10 to obtain a noble metal-amino acid complex solution.
3. Adding acid-treated activated carbon into the noble metal-amino acid complex solution, dipping, pouring out supernatant, adding the aqueous solution of the cocatalyst component, dipping, pouring out supernatant, and freeze-drying to obtain the ultra-low-content noble metal composite catalyst.
In the step 1, the acid is any one of hydrochloric acid, nitric acid and phosphoric acid.
In the step 2, the soluble salt of the noble metal is any one of chloroauric acid, ruthenium trichloride and chloropalladic acid.
In the step 3, the specific process of freeze drying is as follows: and placing the impregnated catalyst in a freeze drying box, pre-freezing for 1-3 h, vacuumizing to below 20Pa, and freeze drying for 6-12 h to obtain the ultralow-content noble metal compound catalyst.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts the amino acid complexing impregnation and freeze drying technology, the prepared catalyst has excellent catalytic activity and selectivity and long service life in the acetylene hydrochlorination reaction, the performance is superior to the existing mercury chloride catalyst, and the acetylene conversion rate can be kept to be more than 98.5 percent and the vinyl chloride selectivity can be kept to be more than 99 percent in long-time operation.
2. The ultralow-content precious metal composite catalyst prepared by the invention is renewable and recyclable, green, pollution-free and environment-friendly, and avoids the pollution of mercury-containing catalysts to the environment. The compounding of a plurality of metal active components can further improve the performance of the catalyst, delay the attenuation of the catalyst and reduce the production cost to a certain extent.
3. The preparation method adopts a continuous impregnation method, the noble metal-amino acid complex and the cocatalyst component are continuously impregnated on the acid-treated activated carbon carrier, the steps of filtering, drying, roasting and the like are not needed in the middle, the process route is greatly simplified, the industrial production is easy to realize, and the added value of the product is high.
Drawings
FIG. 1 is a graph of the operating life of the catalyst prepared in example 1.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
1. Washing columnar coconut shell activated carbon with tap water for several times to remove surface impurity ash, slowly adding the columnar coconut shell activated carbon into a nitric acid aqueous solution with the mass fraction of 10%, and heating and boiling for 1 h. And after cooling, repeatedly soaking and washing with deionized water until the pH value of the washing liquid is more than 4, and finally drying in a blast drying oven at 120 ℃ to obtain the acid-treated columnar coconut shell activated carbon.
2. According to the molar ratio of the chloroauric acid to the cysteine of 1:10, 0.2mL of 0.25mol/L chloroauric acid aqueous solution is put into a beaker, deionized water is added to dilute the chloroauric acid aqueous solution to 20mL, 5mL of 0.1mol/L cysteine aqueous solution is added dropwise, turbidity appears at the beginning, and precipitates are dissolved after the chloroauric acid aqueous solution is added dropwise to excess to obtain the gold-cysteine complex solution.
3. According to the mass content of gold and copper chloride in the catalyst of 0.1% and 0.27%, 10g of acid-treated columnar coconut shell activated carbon is added into the gold-cysteine complex solution obtained in the step 2 to be soaked for 2h, then the supernatant is poured out, and then 2mL of 0.1mol/L copper chloride aqueous solution is added to be soaked for 2 h. And placing the impregnated catalyst in a freeze drying box, pre-freezing for 2h, vacuumizing to below 20Pa, freeze drying for 12h to obtain the ultralow-content noble metal composite catalyst, and sealing and storing.
Example 2
1. Washing flaky coconut shell activated carbon with tap water for several times to remove surface impurity ash, slowly adding the flaky coconut shell activated carbon into a nitric acid aqueous solution with the mass fraction of 10%, and heating and boiling for 1 h. And after cooling, repeatedly soaking and washing with deionized water until the pH value of the washing liquid is more than 4, and finally drying in a blast drying oven at 120 ℃ to obtain the acid-treated flaky coconut shell activated carbon.
2. According to the molar ratio of the chloroauric acid to the glutamine of 1:10, 0.1mL of 0.25mol/L chloroauric acid aqueous solution is put into a beaker, deionized water is added to dilute the chloroauric acid aqueous solution to 20mL, then 2.5mL of 0.1mol/L glutamine aqueous solution is added dropwise, turbidity appears at the beginning, and precipitates are dissolved after the chloroauric acid aqueous solution is added dropwise to excess, so that the gold-glutamine complex solution is obtained.
3. According to the mass content of gold in the catalyst of 0.05% and the mass content of cerium chloride of 0.49%, 10g of acid-treated flaky coconut shell activated carbon is added into the gold-glutamine complex solution obtained in the step 2 to be soaked for 2h, then the supernatant is poured out, and then 2mL of 0.1mol/L cerium chloride aqueous solution is added to be soaked for 2 h. And placing the impregnated catalyst in a freeze drying box, pre-freezing for 1h, vacuumizing to below 20Pa, freeze drying for 6h to obtain the ultralow-content noble metal composite catalyst, and sealing and storing.
Example 3
1. The columnar wood activated carbon is washed for a plurality of times by tap water to remove surface impurity ash, and then is slowly added into a nitric acid water solution with the mass fraction of 20 percent, and is heated and boiled for 1 h. And after cooling, repeatedly soaking and washing with deionized water until the pH value of the washing liquid is more than 4, and finally drying in a blast drying oven at 120 ℃ to obtain the acid-treated columnar wood activated carbon.
2. According to the molar ratio of the chloroauric acid to the cysteine of 1:8, 0.5mL of 0.25mol/L chloroauric acid aqueous solution is put into a beaker, deionized water is added to dilute the chloroauric acid aqueous solution to 20mL, 10mL of 0.1mol/L cysteine aqueous solution is added dropwise, turbidity appears at the beginning, and precipitates are dissolved after the chloroauric acid aqueous solution is added dropwise to excess to obtain the gold-cysteine complex solution.
3. According to the catalyst, the mass content of gold is 0.25%, the total mass content of copper chloride and cobalt chloride is 0.53%, 10g of acid-treated columnar wood activated carbon is added into the gold-cysteine complex solution obtained in the step 2 to be soaked for 2h, then the supernatant is poured out, and then 5mL of 0.1mol/L copper chloride aqueous solution and 5mL0.1mol/L cobalt chloride aqueous solution are added to be soaked for 2 h. And placing the impregnated catalyst in a freeze drying box, pre-freezing for 3h, vacuumizing to below 20Pa, freeze drying for 12h to obtain the ultralow-content noble metal composite catalyst, and sealing and storing.
Example 4
1. The columnar coal activated carbon is washed for a plurality of times by tap water to remove surface impurity ash, and then slowly added into a hydrochloric acid aqueous solution with the mass fraction of 10%, and heated and boiled for 1 h. And after cooling, repeatedly soaking and washing with deionized water until the pH value of the washing liquid is more than 4, and finally drying in a blast drying oven at 120 ℃ to obtain the acid-treated columnar coal activated carbon.
2. According to the molar ratio of ruthenium chloride to cysteine of 1:10, 0.2mL of 0.25mol/L ruthenium trichloride aqueous solution is taken to be placed in a beaker, deionized water is added to be diluted to 20mL, then 5mL of 0.1mol/L cysteine aqueous solution is added dropwise, turbidity appears at the beginning, and precipitates are dissolved after the dropwise addition is carried out to excess, so that the ruthenium-cysteine complex solution is obtained.
3. According to the mass content of ruthenium in the catalyst of 0.1 percent and the total mass content of copper chloride and bismuth chloride of 0.90 percent, 10g of acid-treated columnar coal activated carbon is added into the ruthenium-cysteine complex solution obtained in the step 2 for soaking for 2 hours, then the supernatant is poured out, and then 2mL of 0.1mol/L copper chloride aqueous solution and 2mL of 0.1mol/L bismuth chloride aqueous solution are added for soaking for 2 hours. And placing the impregnated catalyst in a freeze drying box, pre-freezing for 2h, vacuumizing to below 20Pa, freeze drying for 12h to obtain the ultralow-content noble metal composite catalyst, and sealing and storing.
Example 5
1. The columnar coal activated carbon is washed for a plurality of times by tap water to remove surface impurity ash, and then slowly added into a hydrochloric acid aqueous solution with the mass fraction of 10%, and heated and boiled for 1 h. And after cooling, repeatedly soaking and washing with deionized water until the pH value of the washing liquid is more than 4, and finally drying in a blast drying oven at 120 ℃ to obtain the acid-treated columnar coal activated carbon.
2. According to the molar ratio of chloropalladic acid to asparagine of 1:10, 0.2mL of 0.25mol/L chloropalladic acid aqueous solution is put into a beaker, deionized water is added to dilute the solution to 20mL, then 5mL of 0.1mol/L asparagine aqueous solution is added dropwise, turbidity appears at the beginning, and precipitates are dissolved after the dropwise addition is carried out to excess, so that the palladium-asparagine complex solution is obtained.
3. According to the mass content of palladium in the catalyst of 0.1 percent and the total mass content of copper chloride and cesium chloride of 0.61 percent, 10g of acid-treated columnar coal activated carbon is added into the palladium-asparagine complex solution obtained in the step 2 for soaking for 2 hours, then the supernatant is poured out, and then 2mL of 0.1mol/L copper chloride aqueous solution and 2mL of 0.1mol/L cesium chloride aqueous solution are added for soaking for 2 hours. And placing the impregnated catalyst in a freeze drying box, pre-freezing for 2h, vacuumizing to below 20Pa, freeze drying for 12h to obtain the ultralow-content noble metal composite catalyst, and sealing and storing.
Example 6
1. The spherical wood activated carbon is washed for several times by tap water to remove surface impurity ash, and then slowly added into a phosphoric acid aqueous solution with the mass fraction of 5%, and heated and boiled for 1 h. And after cooling, repeatedly soaking and washing with deionized water until the pH value of the washing liquid is more than 4, and finally drying in a blast drying oven at 120 ℃ to obtain the acid-treated spherical wood activated carbon.
2. According to the molar ratio of chloroauric acid to glutamine of 1:2, 0.1mL of 0.25mol/L chloroauric acid aqueous solution is taken to be put in a beaker, deionized water is added to be diluted to 20mL, then 0.5mL of 0.1mol/L glutamine aqueous solution is added dropwise, turbidity appears at the beginning, and precipitates are dissolved after excessive addition to obtain the gold-glutamine complex solution.
3. According to the catalyst, 10g of acid-treated spherical wood activated carbon is added into the gold-glutamine complex solution obtained in the step 2 to be soaked for 2 hours according to the mass content of gold in the catalyst being 0.05% and the total mass content of cerium chloride being 0.06%, the supernatant is poured out, and then 0.25mL of 0.1mol/L cerium chloride aqueous solution is added to be soaked for 2 hours. And placing the impregnated catalyst in a freeze drying box, pre-freezing for 1h, vacuumizing to below 20Pa, freeze drying for 6h to obtain the ultralow-content noble metal composite catalyst, and sealing and storing.
Example 7
1. Washing columnar coconut shell activated carbon with tap water for several times to remove surface impurity ash, slowly adding the columnar coconut shell activated carbon into a nitric acid aqueous solution with the mass fraction of 10%, and heating and boiling for 1 h. And after cooling, repeatedly soaking and washing with deionized water until the pH value of the washing liquid is more than 4, and finally drying in a blast drying oven at 120 ℃ to obtain the acid-treated columnar coconut shell activated carbon.
2. According to the molar ratio of the chloroauric acid to the cysteine of 1:10, 0.2mL of 0.25mol/L chloroauric acid aqueous solution is put into a beaker, deionized water is added to dilute the chloroauric acid aqueous solution to 20mL, 5mL of 0.1mol/L cysteine aqueous solution is added dropwise, turbidity appears at the beginning, and precipitates are dissolved after the chloroauric acid aqueous solution is added dropwise to excess to obtain the gold-cysteine complex solution.
3. According to the catalyst, the mass content of gold is 0.1%, the total mass content of copper chloride, cerium chloride and cobalt chloride is 0.65%, 10g of acid-treated columnar coconut shell activated carbon is added into the gold-cysteine complex solution obtained in the step 2 to be soaked for 2 hours, then the supernatant is poured out, and then 2mL of 0.1mol/L copper chloride aqueous solution, 1mL of 0.1mol/L cerium chloride aqueous solution and 1mL of 0.1mol/L cobalt chloride aqueous solution are added to be soaked for 2 hours. And placing the impregnated catalyst in a freeze drying box, pre-freezing for 2h, vacuumizing to below 20Pa, freeze drying for 12h to obtain the ultralow-content noble metal composite catalyst, and sealing and storing.
In order to prove the beneficial effects of the invention, the inventor uses the ultralow-content noble metal composite catalyst prepared in the examples 1-7 in acetylene hydrochlorination reaction, and adopts a fixed bed reactor to continuously evaluate the acetylene hydrochlorination reaction. Raw materials of acetylene gas and hydrogen chloride gas come from a high-pressure steel cylinder, the flow rate of the raw materials is regulated by a mass flow meter, the raw materials are mixed and enter a reactor, the temperature of the reactor is controlled by a temperature program controller, and reaction products are absorbed by alkali liquor and then are subjected to online monitoring analysis by a gas chromatograph. The test is carried out at the acetylene volume space velocity of 250h-1The flow rate ratio of hydrogen chloride to acetylene was 1.1, and the temperature was 180 ℃, and the test results are shown in table 1.
Table 1 test results of compounded catalysts prepared in examples 1-7
| Examples | Initial acetylene conversion | Initial vinyl chloride selectivity | Acetylene for the first 10hAverage decay Rate of conversion |
| 1 | 87.6％ | 99.9％ | 0.1055％ |
| 2 | 79.1％ | 99.8％ | 0.1331％ |
| 3 | 92.2％ | 99.9％ | 0.0852％ |
| 4 | 79.0％ | 97.3％ | 0.3819％ |
| 5 | 62.5％ | 91.6％ | 0.6135％ |
| 6 | 72.8％ | 99.8％ | 0.2086％ |
| 7 | 86.3％ | 99.9％ | 0.0988％ |
As can be seen from Table 1, the composite catalyst prepared by the invention can efficiently catalyze the hydrochlorination of acetylene in 250h-1The initial acetylene conversion rate can reach more than 90 percent at high space velocity, the decay rate of the acetylene conversion rate can be lower than 0.1 percent/h, and the selectivity of the chloroethylene can be maintained at more than 99.9 percent. The composite catalyst prepared by the invention is renewable and recyclable, is green, pollution-free and environment-friendly, is easy to realize industrial production by adopting a continuous impregnation method, and has high added value of products.
Meanwhile, the inventor tests the service life of the complex catalyst prepared in the example 1, and the service life experiment is carried out when the volume space velocity of acetylene is 50h-1The other conditions are the same as before. Experimental data for acetylene conversion were collected as shown in figure 1. As can be seen from FIG. 1, the acetylene conversion rate can be maintained above 99% basically as the reaction continues, especially the acetylene conversion rate can be kept stable after the catalyst reacts for 1000h, which shows that the composite catalyst of the present invention can maintain higher activity in the reaction process for a longer time.
The above description is only for the preferred embodiment of the present invention and should not be taken as limiting the invention. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (9)
1. An ultra-low content noble metal composite catalyst for acetylene hydrochlorination reaction is characterized in that: the catalyst takes acid-treated active carbon as a carrier, and a noble metal-amino acid complex and a cocatalyst component are loaded, wherein the amino acid is any one of cysteine, glutamine and asparagine or any one of derivatives thereof, and the cocatalyst component is any one or more than two of copper chloride, cobalt chloride, cerium chloride, bismuth chloride and cesium chloride; the mass content of the noble metal in the catalyst is 0.05-0.25%, and the mass content of the cocatalyst component is 0.06-0.90%;
the preparation method of the noble metal composite catalyst comprises the following steps:
(1) washing activated carbon with tap water to remove surface impurity ash, then adding the activated carbon into an acid aqueous solution with the mass fraction of 5-20%, heating and boiling for 1h, cooling, repeatedly soaking and washing with deionized water until the pH value of a washing liquid is more than 4, and drying to obtain acid-treated activated carbon;
(2) dropwise adding an amino acid aqueous solution into the aqueous solution of the noble metal soluble salt according to the molar ratio of the noble metal soluble salt to the amino acid of 1: 2-10 to obtain a noble metal-amino acid complex solution;
(3) adding acid-treated activated carbon into the noble metal-amino acid complex solution, dipping, pouring out supernatant, adding the aqueous solution of the cocatalyst component, dipping, pouring out supernatant, and freeze-drying to obtain the ultra-low-content noble metal composite catalyst.
2. The ultra-low content noble metal composite catalyst for hydrochlorination of acetylene according to claim 1, characterized in that: the mass content of the noble metal in the catalyst is 0.1-0.2%, and the mass content of the cocatalyst component is 0.25-0.65%.
3. The ultra-low content noble metal composite catalyst for hydrochlorination of acetylene according to claim 1 or 2, characterized in that: the noble metal is any one of gold, ruthenium and palladium.
4. The ultra-low content noble metal composite catalyst for hydrochlorination of acetylene according to claim 1 or 2, characterized in that: the noble metal is gold.
5. The ultra-low content noble metal composite catalyst for hydrochlorination of acetylene according to claim 4, characterized in that: the cocatalyst component is any one or more than two of copper chloride, cobalt chloride and cerium chloride.
6. The ultra-low content noble metal composite catalyst for hydrochlorination of acetylene according to claim 1, characterized in that: the active carbon is any one of wood active carbon, coconut shell active carbon and coal active carbon, and the shape of the active carbon is any one of column, sheet and sphere.
7. The ultra-low content noble metal composite catalyst for hydrochlorination of acetylene according to claim 1, characterized in that: in the step (1), the acid is any one of hydrochloric acid, nitric acid and phosphoric acid.
8. The ultra-low content noble metal composite catalyst for hydrochlorination of acetylene according to claim 1, characterized in that: in the step (2), the soluble salt of the noble metal is any one of chloroauric acid, ruthenium trichloride and chloropalladite.
9. The ultra-low content noble metal composite catalyst for hydrochlorination of acetylene according to claim 1, characterized in that: in the step (3), the specific process of freeze drying is as follows: and placing the impregnated catalyst in a freeze drying box, pre-freezing for 1-3 h, vacuumizing to below 20Pa, and freeze drying for 6-12 h to obtain the ultralow-content noble metal compound catalyst.
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| GB201908844D0 (en) * | 2019-06-20 | 2019-08-07 | Johnson Matthey Plc | Gold containing catalyst, method of preparation and use |
| CN110548499A (en) * | 2019-08-16 | 2019-12-10 | 西安凯立新材料股份有限公司 | Composite carrier catalyst for acetylene hydrochlorination and application thereof |
| CN110586200B (en) * | 2019-10-08 | 2022-08-12 | 西安凯立新材料股份有限公司 | Regeneration method of gold-carbon catalyst for acetylene hydrochlorination |
| CN112570043B (en) * | 2020-12-08 | 2023-08-01 | 西安凯立新材料股份有限公司 | Catalyst for hydrochlorination of acetylene and application thereof |
| CN113663740A (en) * | 2021-07-28 | 2021-11-19 | 新疆至臻化工工程研究中心有限公司 | Passivation type ultralow-content gold catalyst |
| CN113634283B (en) * | 2021-08-02 | 2023-06-30 | 西安凯立新材料股份有限公司 | Copper-based composite catalyst and method for hydrochlorination of acetylene |
| CN113816823A (en) * | 2021-11-22 | 2021-12-21 | 山东新龙节能环保设备有限公司 | Process for synthesizing chloroethylene by using mercury-free catalyst |
| CN115555037A (en) * | 2022-10-26 | 2023-01-03 | 西安凯立新材料股份有限公司 | Catalyst for acetylene hydrochlorination, gold-based catalyst, preparation method and evaluation method |
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| CN101947465A (en) * | 2010-09-03 | 2011-01-19 | 清华大学 | Mercury-free catalyst with low bullion content for acetylene hydrochlorination and application thereof |
| CN102794174A (en) * | 2011-05-24 | 2012-11-28 | 代斌 | Au-La catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene and preparation method thereof |
| CN103623837B (en) * | 2012-08-24 | 2016-01-06 | 天津市天地创智科技发展有限公司 | The Ru-Co-Cu catalyst of acetylene hydrochlorination synthesizing chloroethylene |
| CN103894208B (en) * | 2012-12-25 | 2016-07-06 | 中国科学院大连化学物理研究所 | For the low noble metal catalyst without mercury of acetylene hydrochlorination reaction, its preparation method and application |
| CN103191760B (en) * | 2013-04-25 | 2015-10-28 | 新疆天业（集团）有限公司 | A kind of Acetylene-hydrochlorlow-content low-content gold compound catalyst |
| CN103272619A (en) * | 2013-06-07 | 2013-09-04 | 天津大学 | Anion modified mercury-free catalyst for ethyne hydrochlorination reaction, and preparation method thereof |
| CN103386315A (en) * | 2013-08-12 | 2013-11-13 | 湖北随州双星生物科技有限公司 | Environment-friendly non-mercury catalyst for acetylene-method chloroethylene synthesis and preparation method thereof |
| CN103962131A (en) * | 2014-05-21 | 2014-08-06 | 新疆大学 | Preparation method of mercury-free catalyst for use in hydrochlorination of acetylene |
| CN104001549B (en) * | 2014-06-09 | 2016-08-24 | 南开大学 | A kind of preparation method of the Au-based catalyst of the high temperature resistance inactivation for synthesizing vinyl chloride |
| CN104801345B (en) * | 2015-03-31 | 2017-09-29 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of support type catalyst without mercury for producing vinyl chloride by acetylene hydrochlorination |
| CN105126833A (en) * | 2015-07-28 | 2015-12-09 | 浙江工业大学 | Ruthenium-carbon catalyst and its use in acetylene hydrochlorination preparation of vinyl chloride |
| CN107803222B (en) * | 2017-09-29 | 2020-06-09 | 浙江工业大学 | Ruthenium complex catalyst for acetylene hydrochlorination |
| CN108262072B (en) * | 2017-12-08 | 2020-06-12 | 石河子大学 | Ruthenium complex catalyst for acetylene hydrochlorination and preparation method and application thereof |
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