CN114029069A - Ionic liquid modified gold-copper acetylene hydrochlorination catalyst and preparation method thereof - Google Patents
Ionic liquid modified gold-copper acetylene hydrochlorination catalyst and preparation method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0288—Phosphorus
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0291—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
Abstract
The invention provides an ionic liquid modified gold-copper acetylene hydrochlorination catalyst and a preparation method thereof, belonging to the technical field of organic synthesis. The catalyst comprises a carrier, an active component and an auxiliary agent, wherein the active carbon is used as the carrier, the gold salt is used as the active component, the copper salt and the ionic liquid are used as the catalyst auxiliary agent, and the addition of the copper salt and the ionic liquid obviously inhibits the reduction of high-valence gold species, reduces the loss of the gold species and improves the stability and the catalytic activity of the catalyst; the catalyst provided by the invention is simple to prepare, has no pollution and high catalytic activity, and is an effective mercury-free catalyst.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to an ionic liquid modified gold-copper acetylene hydrochlorination catalyst and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is one of three major plastics in the world, has the advantages of low cost, strong durability, good physical and chemical properties and the like, is accepted and accepted by more and more people, vinyl chloride is a raw material for synthesizing polyvinyl chloride, the methods for synthesizing vinyl chloride mainly comprise 3 methods, namely an acetylene method, an ethylene method and an ethane method, and currently, the industrial methods mainly comprise the acetylene method taking coal as the raw material and the ethylene method taking petroleum as the raw material. In recent years, the living space and profit space of the calcium carbide acetylene method are expanding continuously, and the calcium carbide acetylene method gradually becomes the best path for producing polyvinyl chloride on a large scale.
The ionic liquid has the advantages of good hydrochloric acid dissolving performance, ionic conductivity, extremely low vapor pressure and the like, and can solve the problems of reduction, carbon deposition and the like of active components of a metal catalyst in acetylene hydrochlorination to a certain extent. Zhang et al, 0.3% Au-10% IL/AC catalyst is prepared by utilizing ionic liquid trimethyl sulfone iodide, wherein the addition of IL can effectively inhibit carbon deposition, simultaneously improve the dispersity of gold, inhibit gold particle aggregation and the adsorption amount to hydrochloric acid in the preparation and reaction processes, stabilize high-valence state gold species in the preparation and reaction processes, and further improve the stability of the catalyst.
The research and development of the mercury-free catalyst are mainly two kinds of metal catalysts with noble metals such as Au, Pd, Ru and the like and non-noble metals such as Bi, Sn, Cu and the like as active centers. In the patent CN112156809A, Au metal is compounded as an active component, and the initial activity of the catalyst can reach 71.2% by modifying with ionic liquid, but the stability of the catalyst can not meet the requirement.
Therefore, it is required to develop an ionic liquid modified gold-copper acetylene hydrochlorination catalyst with high catalytic efficiency and good stability.
Disclosure of Invention
Based on the problems in the prior art, the invention aims to provide an ionic liquid modified gold-copper acetylene hydrochlorination catalyst and a preparation method thereof.
The specific technical scheme of the invention is as follows:
in one aspect, the invention provides an ionic liquid modified gold-copper acetylene hydrochlorination catalyst, which comprises a carrier, an active component and an auxiliary agent;
the carrier is activated carbon;
the activated carbon is wood activated carbon or coconut shell activated carbon;
the specific surface area of the charcoal activated carbon or the coconut shell activated carbon is 800-2/g。
The active component is gold salt;
the gold salt is one of gold chloride or gold thiosulfate;
the gold chloride is selected from one of chloroauric acid, triphenylphosphine chloroauric acid and chlorine (trimethylphosphine) gold;
the gold thiosulfate is selected from one of gold (I) thiosulfate sodium hydrate and aurous ammonium thiosulfate.
The weight of the gold accounts for 0.05-0.2% of the weight of the catalyst.
The auxiliary agent is copper salt and ionic liquid;
the metal copper salt is copper chloride;
the copper chloride is selected from one of copper chloride, cuprous chloride or dilithium tetrachlorocuprate.
The weight of the copper accounts for 0.5-2% of the weight of the catalyst.
The ionic liquid is selected from one or more of acetonyl triphenyl phosphonium chloride, tetraphenyl phosphonium bromide, tetraphenyl phosphonium chloride, 1-allyl 3-methylimidazolium chloride, 1-butyl 3-methylimidazolium dicyanamide salt and 1-butyl 3-methylimidazolium chloride salt.
The weight of the ionic liquid accounts for 1-10% of the weight of the gold-copper acetylene hydrochlorination catalyst.
On the other hand, the invention also provides a preparation method of the ionic liquid modified gold-copper acetylene hydrochlorination catalyst, which comprises the following steps:
(1) crushing and screening active carbon, and then carrying out acid washing, filtering and drying on the active carbon to obtain an active carbon precursor;
(2) preparing a mixed solution of gold salt and copper salt, performing isometric impregnation on the activated carbon precursor by using the mixed solution, and drying to obtain a gold-copper catalyst;
(3) preparing an ionic liquid solution, performing isometric impregnation on the gold-copper catalyst by using the ionic liquid solution, and drying to obtain the ionic liquid modified gold-copper acetylene hydrochlorination catalyst.
The acid washing in the step (1) is as follows: and (3) carrying out acid washing treatment on the activated carbon by adopting a 5-10% HCl solution for 4-10 h.
The drying temperature in the step (1) is 100-120 ℃; the drying time is 6-12 h.
The temperature of the equal-volume impregnation in the step (2) is 24-25 ℃, and the impregnation time is 2-5 h; the drying temperature is 100-120 ℃, and the drying time is 10-20 h.
The concentration ratio of the gold salt to the copper salt in the step (2) is 1-4: 5-10;
preferably, the concentration ratio of the gold salt to the copper salt is 1: 5;
the concentration of the ionic liquid is 10% -30%, and the concentration of the ionic liquid is preferably 20%.
The invention provides application of the catalyst in acetylene hydrochlorination.
The application conditions are that T is 160-2H2)＝180-720h-1、n(HCl):n(C2H2)＝1.05-1.25。
Compared with the prior art, the invention has the beneficial effects that:
(1) the catalyst provided by the invention takes active carbon as a carrier and is prepared by a co-impregnation method; the gold salt is used as an active component, the copper salt and the ionic liquid are used as catalyst auxiliaries, and the addition of the copper salt and the ionic liquid obviously inhibits the reduction of high-valence gold species, reduces the loss of the gold species, and improves the stability and catalytic activity of the catalyst;
(2) the catalyst provided by the invention is simple to prepare, has no pollution and high catalytic activity, and is an effective mercury-free catalyst.
Detailed Description
The following is a more specific example description of the catalyst.
Example 1 an ionic liquid modified gold-copper acetylene hydrochlorination catalyst
The preparation method comprises the following steps:
(1) weighing 50g of wood activated carbon, immersing the activated carbon for 5 hours by using 200mL of 5% wt hydrochloric acid solution, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, and drying the activated carbon for 8 hours at 120 ℃ to obtain an activated carbon precursor;
(2) weighing 40g of activated carbon precursor, dissolving 2.5g of hydrated copper chloride and 0.08g of chloroauric acid in 30mL of deionized water, dropwise adding the solution into the activated carbon precursor, soaking for 4 hours, and transferring the solution into an oven to dry for 12 hours at 120 ℃ to obtain a gold-copper catalyst;
(3) weighing 2g of 1-butyl 3-methylimidazolium chloride, dissolving in 30mL of deionized water, dropwise adding into a gold-copper catalyst, soaking for 4 hours, transferring into an oven, and drying at 120 ℃ for 12 hours to obtain the ionic liquid modified gold-copper acetylene hydrochlorination catalyst.
The catalyst is evaluated at a temperature of 180 ℃ and a space velocity of 180h-1The feed gas C2H2The initial acetylene conversion rate is 95.5 percent, the vinyl chloride selectivity is more than 99.5 percent, the reaction is operated for 800 hours, and the catalyst acetylene conversion rate is 87.5 percent.
Example 2 an ionic liquid modified gold-copper acetylene hydrochlorination catalyst
The preparation method comprises the following steps:
(1) weighing 50g of wood activated carbon, immersing the activated carbon for 5h by using 200mL of 5% wt hydrochloric acid solution, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, and drying the activated carbon for 8h at 120 ℃ to obtain an activated carbon precursor;
(2) weighing 40g of activated carbon precursor, dissolving 2.5g of hydrated copper chloride and 0.08g of chloroauric acid in 30mL of deionized water, dropwise adding the solution into the activated carbon precursor, soaking for 4 hours, and transferring the solution into an oven to dry for 12 hours at 120 ℃ to obtain a gold-copper catalyst;
(3) weighing 2g of 1-butyl 3-methylimidazolium dicyanamide salt, dissolving in 30mL of deionized water, dropwise adding into a gold-copper catalyst, soaking for 4 hours, transferring into an oven, and drying at 120 ℃ for 12 hours to obtain the ionic liquid modified gold-copper acetylene hydrochlorination catalyst.
The catalyst is evaluated at a temperature of 180 ℃ and a space velocity of 180h-1The feed gas C2H2The initial acetylene conversion rate is 94.5 percent, the vinyl chloride selectivity is more than 99.5 percent, the reaction is operated for 800 hours, and the catalyst acetylene conversion rate is 80.1 percent.
Example 3 an ionic liquid modified gold-copper acetylene hydrochlorination catalyst
The preparation method comprises the following steps:
(1) weighing 50g of coconut shell activated carbon, immersing the activated carbon for 5h by using 200mL of 5% wt hydrochloric acid solution, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, and drying the activated carbon for 8h at 120 ℃ to obtain an activated carbon precursor;
(2) weighing 40g of the obtained activated carbon precursor, dissolving 2.5g of hydrated copper chloride and 0.08g of chloroauric acid in 30mL of deionized water, dropwise adding the solution into the obtained activated carbon precursor, soaking for 4 hours, and transferring the solution into an oven to dry for 12 hours at 120 ℃ to obtain a gold-copper catalyst;
(3) weighing 2.8g of tetraphenylphosphonium chloride, dissolving in 30mL of deionized water, dropwise adding into a gold-copper catalyst, soaking for 4 hours, transferring into an oven, and drying at 120 ℃ for 12 hours to obtain the ionic liquid modified gold-copper acetylene hydrochlorination catalyst.
The catalyst is evaluated at a temperature of 180 ℃ and a space velocity of 180h-1The feed gas C2H2The initial acetylene conversion is 92.5 percent, the vinyl chloride selectivity is more than 99.5 percent, the reaction is operated for 800 hours, and the catalyst acetylene conversion is 81.1 percent.
Example 4 an ionic liquid modified gold-copper acetylene hydrochlorination catalyst
The preparation method comprises the following steps:
(1) weighing 50g of wood activated carbon, immersing the activated carbon for 5h by using 200mL of 5% wt hydrochloric acid solution, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, and drying the activated carbon for 8h at 120 ℃ to obtain an activated carbon precursor;
(2) weighing 40g of activated carbon precursor, dissolving 2.5g of hydrated copper chloride and 0.08g of chloroauric acid in 30mL of deionized water, dropwise adding the solution into the activated carbon precursor, soaking for 4 hours, and transferring the solution into an oven to dry for 12 hours at 120 ℃ to obtain a gold-copper catalyst;
(3) weighing 2g of tetraphenylphosphonium bromide, dissolving in 30mL of deionized water, dropwise adding into a gold-copper catalyst, soaking for 4 hours, transferring into an oven, and drying at 120 ℃ for 12 hours to obtain the ionic liquid modified gold-copper acetylene hydrochlorination catalyst.
The catalyst is evaluated at a temperature of 180 ℃ and a space velocity of 180h-1The feed gas C2H2The initial acetylene conversion rate is 95.5 percent, the vinyl chloride selectivity is more than 99.6 percent, the reaction is operated for 800 hours, and the catalyst acetylene conversion rate is 82.7 percent.
Example 5 an ionic liquid modified gold-copper acetylene hydrochlorination catalyst
The preparation method comprises the following steps:
(1) weighing 50g of wood activated carbon, immersing the activated carbon for 5h by using 200mL of 5% wt hydrochloric acid solution, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, and drying the activated carbon for 8h at 120 ℃ to obtain an activated carbon precursor;
(2) weighing 40g of activated carbon precursor, dissolving 2.5g of hydrated copper chloride and 0.08g of chloroauric acid in 30mL of deionized water, dropwise adding the solution into the activated carbon precursor, soaking for 4 hours, and transferring the solution into an oven to dry for 12 hours at 120 ℃ to obtain a gold-copper catalyst;
(3) weighing 2g of tetraphenylphosphonium bromide, dissolving in 30mL of deionized water, dropwise adding into a gold-copper catalyst, soaking for 4 hours, transferring into an oven, and drying at 120 ℃ for 12 hours to obtain the ionic liquid modified gold-copper acetylene hydrochlorination catalyst.
The catalyst is evaluated at a temperature of 180 ℃ and a space velocity of 180h-1The feed gas C2H2The initial acetylene conversion rate is 95.5 percent, the vinyl chloride selectivity is more than 99.6 percent, the reaction is operated for 800 hours, and the catalyst acetylene conversion rate is 82.7 percent.
Example 6 an ionic liquid modified gold-copper acetylene hydrochlorination catalyst
The preparation method comprises the following steps:
(1) weighing 50g of coconut shell activated carbon, immersing the activated carbon for 5h by using 200mL of 5% wt hydrochloric acid solution, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, and drying the activated carbon for 8h at 120 ℃ to obtain an activated carbon precursor;
(2) weighing 40g of the obtained activated carbon precursor, weighing 2.5g of hydrated copper chloride and 0.08g of chloroauric acid, dissolving in 30mL of deionized water, dropwise adding into the activated carbon precursor, soaking for 4 hours, and transferring into an oven to dry at 120 ℃ for 12 hours to obtain a gold-copper catalyst;
(3) weighing 2g of acetonyl triphenyl phosphonium chloride, dissolving in 30mL of deionized water, dropwise adding into a gold-copper catalyst, soaking for 4 hours, transferring into an oven, and drying at 120 ℃ for 12 hours to obtain the ionic liquid modified gold-copper acetylene hydrochlorination catalyst.
The catalyst is evaluated at a temperature of 180 ℃ and a space velocity of 180h-1The feed gas C2H2The initial acetylene conversion rate is 95.8 percent, the vinyl chloride selectivity is more than 99.5 percent, the reaction is operated for 800 hours, and the catalyst acetylene conversion rate is 80.1 percent.
Comparative example 1 a gold-copper acetylene hydrochlorination catalyst
The preparation method comprises the following steps:
weighing 50g of coconut shell activated carbon, immersing the activated carbon for 5h by using 200mL of 5% wt hydrochloric acid solution, washing the activated carbon with deionized water after filtering until the pH value of the aqueous solution is close to 5, and drying the activated carbon for 8h at 120 ℃ to obtain an activated carbon precursor; then taking 40g of activated carbon precursor, weighing 2.5g of hydrated copper chloride and 0.08g of chloroauric acid, dissolving in 30mL of deionized water, dropwise adding into the activated carbon precursor, soaking for 4 hours, transferring into an oven, and drying at 120 ℃ for 12 hours to obtain the gold-copper catalyst.
The catalyst is evaluated at a temperature of 180 ℃ and a space velocity of 180h-1The feed gas C2H2The initial acetylene conversion rate is 95.7 percent, the vinyl chloride selectivity is more than 99.5 percent, the reaction is operated for 800 hours, and the catalyst acetylene conversion rate is 72.1 percent.
Comparative example 2 gold acetylene hydrochlorination catalyst modified by ionic liquid
The preparation method comprises the following steps:
weighing 50g of coconut shell activated carbon, immersing the activated carbon for 5h by using 200mL of 5 wt% hydrochloric acid solution, filtering, washing with deionized water until the pH value of the aqueous solution is close to 5, and drying for 8h at 120 ℃ to obtain an activated carbon precursor; then taking 40g of activated carbon precursor, weighing 0.08g of chloroauric acid, dissolving in 30mL of deionized water, dropwise adding into the activated carbon, dipping for 4 hours, transferring into an oven, drying at 120 ℃ for 12 hours to obtain a gold catalyst, weighing 2g of 1-butyl 3-methylimidazolium chloride, dissolving in 30mL of deionized water, dropwise adding into the gold catalyst, dipping for 4 hours, transferring into the oven, drying at 120 ℃ for 12 hours to obtain the ionic liquid modified gold acetylene hydrochlorination catalyst.
The catalyst is evaluated at a temperature of 180 ℃ and a space velocity of 180h-1The feed gas C2H2HCl 1:1.08, with an initial acetylene conversion of 93.7%, vinyl chloride selectivity greater than 99.5%, the reaction run was 600h, with a catalyst acetylene conversion of 68.9%.
TABLE 1 comparison of catalyst Performance between examples 1-6 and comparative examples 1-2
The following conclusions can be drawn by comparing examples 1 to 6 with comparative examples 1 to 2:
comparison of example 1 with comparative example 1 yields: the catalyst is lack of ionic liquid auxiliary agents, gold salts are used as active components, copper salts are used as auxiliary agents, the activity of the acetylene hydrochlorination reaction is initially high, but the final conversion rate is reduced quickly.
Comparison of example 1 with comparative example 2 yields: the catalyst of example 1 and comparative example 2, which lacks the Cu metal promoter and only Au and the ionic liquid, had the same initial activity, but the catalyst of comparative example 2, which has no Cu metal promoter, had the acetylene conversion rate reduced to 68.9% after 600h of reaction.
The technical scheme of the invention is not limited to the technical means disclosed by the technical means, and also comprises the technical scheme formed by any combination of the technical features. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.
Claims (10)
1. An ionic liquid modified gold-copper acetylene hydrochlorination catalyst is characterized in that: the catalyst comprises a carrier, an active component and an auxiliary agent;
the carrier is activated carbon, and the specific surface area of the activated carbon is 800-1200m2(ii)/g; the active component is gold salt; the auxiliary agent is copper salt and ionic liquid.
2. The gold-copper acetylene hydrochlorination catalyst according to claim 1 characterized in that: the activated carbon is wood activated carbon or coconut shell activated carbon; the gold salt is one of gold chloride or gold thiosulfate; the metal copper salt is copper chloride.
3. The gold-copper acetylene hydrochlorination catalyst according to claim 2 characterized in that:
the gold chloride is selected from one of chloroauric acid, triphenylphosphine chloroauric acid or chlorine (trimethylphosphine) gold;
the gold thiosulfate is selected from one of gold (I) thiosulfate sodium hydrate or aurous ammonium thiosulfate;
the copper chloride is selected from one of copper chloride, cuprous chloride or dilithium tetrachlorocuprate;
the ionic liquid is selected from one or more of acetonyl triphenyl phosphonium chloride, tetraphenyl phosphonium bromide, tetraphenyl phosphonium chloride, 1-allyl 3-methylimidazolium chloride, 1-butyl 3-methylimidazolium dicyanamide salt and 1-butyl 3-methylimidazolium chloride salt.
4. The gold-copper acetylene hydrochlorination catalyst according to claim 2 characterized in that: the weight of the gold accounts for 0.05-0.2% of the weight of the catalyst.
5. The gold-copper acetylene hydrochlorination catalyst according to claim 2 characterized in that: the weight of the copper accounts for 0.5-2% of the weight of the catalyst.
6. The gold-copper acetylene hydrochlorination catalyst according to claim 2 characterized in that: the weight of the ionic liquid accounts for 1-10% of the weight of the gold-copper acetylene hydrochlorination catalyst.
7. The method for producing a gold-copper acetylene hydrochlorination catalyst according to any one of claims 1 to 6, characterized by: the method comprises the following steps:
(1) crushing and screening active carbon, and then carrying out acid washing, filtering and drying on the active carbon to obtain an active carbon precursor;
(2) preparing a mixed solution of a gold salt and a copper salt, performing isometric impregnation on an activated carbon precursor by using the mixed solution, and drying to obtain a gold-copper acetylene hydrochlorination catalyst;
(3) preparing an ionic liquid solution, performing isometric impregnation on the gold-copper catalyst by using the ionic liquid solution, and drying to obtain the ionic liquid modified gold-copper acetylene hydrochlorination catalyst.
8. The method of claim 7, wherein: the temperature of the equal-volume impregnation in the step (2) is 24-25 ℃, and the impregnation time is 2-5 h; the drying temperature is 100-120 ℃, and the drying time is 10-20 h.
9. The method of claim 7, wherein: the concentration ratio of the gold salt to the copper salt in the step (2) is 1-4: 5-10;
the concentration of the ionic liquid is 10-30%.
10. Use of the gold-copper acetylene hydrochlorination catalyst according to any one of claims 1 to 6 and the gold-copper acetylene hydrochlorination catalyst prepared by the preparation method according to any one of claims 7 to 9 in acetylene hydrochlorination reactions.
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| CN115739134A (en) * | 2022-11-24 | 2023-03-07 | 贵州大学 | Method for preparing composite catalyst for vinyl chloride synthesis by using ruthenium trichloride waste |
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| CN106866349A (en) * | 2015-12-14 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of method of low temperature preparing chloroethylene by acetylene hydrochlorination |
| CN112156809A (en) * | 2020-10-20 | 2021-01-01 | 西安凯立新材料股份有限公司 | Ionic liquid modified activated carbon loaded gold catalyst and application thereof in catalyzing acetylene hydrochlorination |
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| CN115739134A (en) * | 2022-11-24 | 2023-03-07 | 贵州大学 | Method for preparing composite catalyst for vinyl chloride synthesis by using ruthenium trichloride waste |
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