CN112007696B - Gold-silver nanocluster catalyst for acetylene hydrochlorination - Google Patents
Gold-silver nanocluster catalyst for acetylene hydrochlorination Download PDFInfo
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Abstract
The invention discloses a gold and silver nanocluster catalyst suitable for acetylene hydrochlorination and a preparation method and application thereof, wherein the catalyst mainly comprises a main active species gold and silver nanocluster and carrier active carbon, and the gold and silver nanocluster accounts for 0.1-3% of the weight of the catalyst. The preparation of the catalyst mainly comprises two steps: 1) synthesizing gold and silver nanoclusters; 2) dispersing the gold and silver nanoclusters synthesized in the step 1) in a mixed solvent, adding a carrier, and loading active species on the carrier through the steps of stirring, centrifuging, filtering, drying and the like to obtain the gold and silver nanocluster catalyst. The gold-silver nanocluster catalyst prepared by the invention is used for acetylene hydrochlorination, shows good catalytic activity and vinyl chloride selectivity, shows excellent stability and can be directly used as a substitute product of a mercury-based catalyst used for acetylene hydrochlorination.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to preparation and application of a gold and silver nanocluster catalyst.
Background
Acetylene hydrochlorination is an important method for producing vinyl chloride monomer at present, and particularly in China rich in coal and lean oil, the vinyl chloride monomer produced by the acetylene hydrochlorination is over 1300 million tons every year. The catalyst used in the traditional acetylene hydrochlorination method is an activated carbon-loaded mercuric chloride catalyst, but the characteristic that mercury metal is easy to lose influences the performance of the catalyst and threatens the ecological environment. With the increasing emphasis on environmental issues, the reduction and gradual prohibition of the use of mercury-based catalysts is an important issue facing the acetylene-process vinyl chloride production enterprises.
The recent endorsement of the Water guarantee convention has in turn brought a regulatory directive on the use of mercury based catalysts and stipulated that by 2020, the use of mercury based catalysts is mandatorily reduced and gradually forbidden. The search for environmentally friendly non-mercury catalysts is therefore a problem that the vinyl chloride synthesis industry is demanding to solve.
The research of colleges and universities and scientific research institutes can be mainly divided into two directions: one is to develop a noble metal catalyst with noble metal as an active center; in addition, a catalyst using non-noble metal as an active center is developed, and although a mercury-free catalyst is in the development stage and no industrial application is reported in China, a series of progresses are made, such as:
patent application No. 201210570613.X discloses a low noble metal mercury-free catalyst used in a reaction for synthesizing vinyl chloride and a preparation method thereof. The composite active component is formed by loading a small amount of metal compounds such as iron, zinc, copper and the like and matching a small amount of noble metals such as gold, palladium, ruthenium, platinum and the like. The catalyst reported by the invention has the characteristics of low content of noble metal, low cost, high activity, long service life and the like.
The patent application No. 201611253836.8 discloses a noble metal-based catalyst for the hydrochlorination of acetylene to vinyl chloride and a preparation method thereof. The activity of the catalyst is increased and the stability of the catalyst is improved by adding other non-noble metals as promoters, the added noble metal salt is chloroauric acid, the content of the noble metal salt is 0.5-20% of the mass of the catalyst, the common metal compounds are copper chloride, magnesium chloride, silver chloride, barium chloride, zinc chloride and the like, the content of the noble metal salt is 0.5-20% of the mass of the catalyst, and the catalyst has high activity and vinyl chloride selectivity but is not subjected to long-time stability test.
The patent application No. 201710858286.0 discloses a method for preparing a noble metal catalyst for vinyl chloride synthesis. The active carbon with more carboxyl and carbonyl on the surface is obtained by carrying out a series of treatments on the carrier active carbon by adding the polymer in situ, which is beneficial to additionally adding an auxiliary agent into the noble metal precursor solution, and the form of metal loading is determined by the auxiliary agent so as to form a stable synergistic system. This improves the stability and uniformity of the noble metal dispersion, and finally the noble metal catalyst is obtained by means of stirring, centrifugation, or the like. The catalyst is used for acetylene hydrochlorination, can realize the acetylene conversion rate of more than 99 percent, has good catalytic effect and the advantage of environmental protection and recoverability, can comprehensively replace the mercury-based catalyst widely used at present, and is suitable for the production of chloroethylene.
The patent with application number 201210100688.1 discloses a gold complex catalyst applied to hydrochlorination of acetylene, the main active component of the catalyst is potassium tetrathiocyanate, the auxiliary active component is one or two of potassium chloride, copper chloride, zinc chloride and cobalt chloride, and the carrier is activated carbon. Wherein the gold complex accounts for 0.1-2.5% of the total weight of the catalyst, and the auxiliary active components account for 0.05-15% of the total weight of the catalyst. The gold complex catalyst prepared by the invention is a novel mercury-free catalyst with good activity, high stability and strong selectivity.
The patent with the application number of 201810682086.9 discloses a copper-based catalyst for synthesizing vinyl chloride through hydrochlorination of acetylene, and a preparation method and application thereof, wherein an organic amide compound is used as a stabilizer of copper salt to prepare the copper-based catalyst, the copper salt is used in a large amount, and the prepared catalyst has good catalytic activity and stability.
At present, the catalyst with the best application prospect is still a gold catalyst, which shows higher activity and selectivity, but as cationic gold is easily reduced by acetylene to be inactivated, the problem of trying to solve the stability of the gold-based catalyst is the key to overcome the industrial application of the gold-based catalyst in the hydrochlorination reaction of acetylene. At present, researchers mainly adopt a method of adding other common metals and ligands to improve the stability of the gold catalyst, but breakthrough progress is not made.
Disclosure of Invention
The research of the invention finds that the nanocluster contains other metals and also contains organic ligands for stabilizing gold, so the research of the application of the nanocluster in the hydrochlorination reaction of acetylene is not only helpful for developing a stable and efficient gold catalyst, but also helpful for deeply understanding the action mechanism of the ligands and the assistant metals on the stable high-valence gold in the hydrochlorination reaction of acetylene. Therefore, the invention provides a gold-based catalyst taking gold and silver nanoclusters as active species, and particularly relates to a catalyst formed by synthesis of the gold and silver nanoclusters and loading of the gold and silver nanoclusters on carrier active carbon, and the catalyst shows good catalytic activity and does not have obvious deactivation phenomenon after 1600-hour online test, and has the potential of directly replacing mercury-based catalysts in the existing acetylene hydrochlorination reaction.
The invention aims to overcome the defects of the existing catalyst for synthesizing vinyl chloride by catalysis, and provides a preparation method of a gold-silver nanocluster catalyst for preparing vinyl chloride by a calcium carbide acetylene method.
The technical scheme of the invention is as follows:
in a first aspect, the invention provides a gold and silver nanocluster catalyst, which takes a gold and silver nanocluster as an active component and takes active carbon as a carrier.
The chemical formula of the gold and silver nanocluster is [ Au ]23@xAgx(S-Adm)15]Wherein x is 4-7; the structure of the gold and silver nanocluster is that a 24-face core consisting of gold and silver atoms covers three Au3(SR)4Structure and an AgS3Structure;
wherein in the chemical formula, S-Adm refers to adamantane thiol; in the formula, SR refers to a thiol ligand.
Preferably, the loading amount of the gold and silver nanoclusters is 0.1-3 wt%.
In a second aspect, the invention provides a preparation method of the gold and silver nanocluster catalyst, which comprises the following steps:
1) dissolving a gold precursor and a silver precursor in a solvent I to obtain a solution I;
2) adding a surfactant into the solution I, and adding a thiol compound serving as a reducing agent and a gold stabilizing agent of high-valence gold while stirring to obtain a dark red solution II;
3) when the solution II is changed from deep red to transparent, adding a reducing agent aqueous solution into the solution II, and continuously stirring for 1-7 days to obtain a solution III;
4) removing the solvent from the solution III by reduced pressure distillation to obtain a crude product, and washing and purifying the crude product by using methanol and acetone;
5) recrystallizing the purified crude product to obtain black crystals, wherein the black crystals are gold and silver nanoclusters;
6) and loading the gold and silver nanoclusters on activated carbon by an impregnation method.
Preferably, the step 6) comprises the steps of:
I. purifying and dispersing the gold and silver nanoclusters into a solvent II to obtain a system I;
II. Adding activated carbon into the system I, and soaking at room temperature;
and III, centrifuging, filtering and drying the impregnated activated carbon to obtain the gold and silver nanocluster catalyst.
Preferably, the gold precursor is chloroauric acid; the silver precursor is silver nitrate; the molar ratio of the gold precursor to the silver precursor is 1: 1-1: 2; the surfactant is one or more of tetrabutylammonium bromide, tetraoctylammonium bromide and tetraethylammonium bromide; the solvent I is a mixed solvent formed by one or more of diethyl ether, acetone, toluene, acetonitrile, methanol, ethanol and dimethyl sulfoxide; the reducing agent is one or more of lithium aluminum hydride, sodium borohydride, potassium borohydride and elementary iodine.
Preferably, the thiol compound is an aromatic or aliphatic compound containing a thiol group; the number of carbons of the thiol compound is 8-12.
Preferably, the thiol compound is octyl thiol having 8 carbon atoms, nonyl thiol having 9 carbon atoms, 1-decyl thiol having 10 carbon atoms, 1-undecyl thiol having 11 carbon atoms, or adamantane thiol having 12 carbon atoms.
Preferably, the solvent II is one or more of ethanol, dichloromethane, dichloroethane, chloroform and acetone.
In a third aspect, the invention applies the catalyst to the reaction of acetylene and hydrogen chloride to synthesize vinyl chloride.
Preferably, the reaction is carried out in a fixed bed reactor; the ratio of acetylene to hydrogen chloride is 1: 1-1: 1.08; the reaction temperature is 150-180 ℃; the reaction pressure is 0.01-0.1 MP; the space velocity of acetylene is 30-200 h-1(ii) a The dosage of the catalyst is 3.0-6.0 g.
The invention has the beneficial effects that:
1. the active component of the catalyst prepared by the invention is a cluster structure formed by the gold and silver ions and the organic ligand, the structure is different from a metal alloy, the sulfur-containing ligand surrounds the structural characteristic of a metal core, so that the gold and silver core has the property of positive valence metal, and due to reasonable electron distribution, the catalyst has outstanding stability in the hydrochlorination reaction of acetylene.
2. The catalyst prepared by the invention needs to synthesize the gold and silver nanoclusters in advance, and aims to provide sufficient conditions for the synthesis of stable clusters, so that the synthesized gold and silver nanoclusters have better stability.
3. The catalyst prepared by the invention shows good catalytic activity and chloroethylene selectivity and excellent stability, the conversion rate of acetylene is basically kept unchanged after 1600h reaction, and the catalyst can be directly used as a substitute product of a mercury-based catalyst used for acetylene hydrochlorination reaction, so that the environmental problem caused by mercury pollution is reduced.
4. The catalyst prepared by the invention has convenient and safe preparation process and is suitable for industrial large-scale production and use.
Drawings
Figure 1 performance of the catalyst provided in example 1 in the hydrochlorination of acetylene;
fig. 2 shows a structural model of the gold and silver nanocluster catalyst prepared by the present invention.
Detailed Description
The raw materials used in the following examples are all conventional products which can be obtained commercially.
Example 1 catalyst preparation
Weighing 133.77mg of chloroauric acid and 66.21mg of silver nitrate, sequentially dissolving in 235ml of acetone, adding 2.06g of tetraoctylammonium bromide, adding 327.98mg of adamantane thiol serving as a reducing agent and a gold stabilizer of high-valence gold while stirring, adding 10ml of sodium borohydride containing 1.38g of the mixture into the solution when the solution is changed from deep red to be transparent, continuously stirring for 7 days, removing the solvent from the obtained mixture through reduced pressure distillation, and washing and purifying the mixture by using methanol and acetone to obtain a crude product; and dissolving the crude product in acetonitrile and toluene for recrystallization to obtain a black crystal which is a high-purity gold and silver nanocluster. Dispersing 50mg of high-purity gold and silver nanoclusters into 200ml of dichloromethane to obtain impregnation liquid containing the gold and silver nanoclusters; weighing 49.95g of activated carbon, and soaking in impregnation liquid containing gold and silver nanoclusters; and centrifuging, filtering and drying the soaked activated carbon to finally obtain the gold and silver nanocluster catalyst.
Example 2 catalyst preparation
Weighing 1.42g of chloroauric acid and 584.03mg of silver nitrate, sequentially dissolving in 2490ml of toluene, adding 12.85g of tetrabutylammonium bromide, adding 3.02g of octanethiol as a reducing agent and a gold stabilizer of high-valence gold while stirring, adding 10ml of potassium borohydride containing 20.34g of potassium hydroxide into the solution when the solution is changed from deep red to be transparent, continuously stirring for 4 days, removing the solvent from the obtained mixture through reduced pressure distillation, and washing and purifying the mixture by using methanol and acetone to obtain a crude product; and dissolving the crude product in acetonitrile and toluene for recrystallization to obtain a black crystal which is a high-purity gold and silver nanocluster. 1.5g of high-purity gold and silver nanoclusters are taken and dispersed into 200ml of dichloroethane to obtain impregnation liquid containing the gold and silver nanoclusters; weighing 48.5g of active carbon and soaking the active carbon in impregnation liquid containing gold and silver nanoclusters; and centrifuging, filtering and drying the soaked activated carbon to finally obtain the gold and silver nanocluster catalyst.
Example 3 catalyst preparation
Weighing 123.56mg of chloroauric acid and 76.44mg of silver nitrate, sequentially dissolving in 217ml of ethanol, adding 1.90g of tetraoctylammonium bromide, adding 288.58mg of nonanethiol as a reducing agent and a gold stabilizer of high-valence gold while stirring, adding 10ml of lithium aluminum hydride containing 1.28g of the solution when the solution is changed from deep red to be transparent, continuously stirring for 6 days, removing the solvent from the obtained mixture through reduced pressure distillation, and washing and purifying with methanol and acetone to obtain a crude product; and dissolving the crude product in acetonitrile and toluene for recrystallization to obtain a black crystal which is a high-purity gold and silver nanocluster. Dispersing 0.1g of high-purity gold and silver nanoclusters into 200ml of chloroform to obtain impregnation liquid containing the gold and silver nanoclusters; weighing 49.9g of active carbon and soaking the active carbon in impregnation liquid containing gold and silver nanoclusters; and centrifuging, filtering and drying the soaked activated carbon to finally obtain the gold and silver nanocluster catalyst.
Example 4 catalyst preparation
Weighing 1.10g of chloroauric acid and 904.06mg of silver nitrate, sequentially dissolving in 1927ml of diethyl ether, adding 6.48g of tetraethylammonium bromide, adding 2.78g of 1-decanethiol as a reducing agent and a gold stabilizer of high-valence gold while stirring, adding 10ml of sodium borohydride containing 11.33g into the solution when the solution becomes transparent from deep red, continuously stirring for 3 days, removing the solvent from the obtained mixture through reduced pressure distillation, and washing and purifying with methanol and acetone to obtain a crude product; and dissolving the crude product in acetonitrile and toluene for recrystallization to obtain a black crystal which is a high-purity gold and silver nanocluster. 0.5g of high-purity gold and silver nanoclusters are taken and dispersed into 200ml of acetone to obtain impregnation liquid containing the gold and silver nanoclusters; weighing 49.5g of active carbon and soaking the active carbon in impregnation liquid containing gold and silver nanoclusters; and centrifuging, filtering and drying the soaked activated carbon to finally obtain the gold and silver nanocluster catalyst.
Example 5 catalyst preparation
Weighing 1.15g of chloroauric acid and 852.17mg of silver nitrate, sequentially dissolving in 2022ml of dimethyl sulfoxide, adding 17.69g of tetraoctylammonium bromide, adding 3.15g of 1-undecanethiol as a reducing agent and a gold stabilizer of high-valence gold while stirring, adding 10ml of elementary iodine containing 79.74g of the solution when the solution is changed from deep red to transparent, continuously stirring for 5 days, removing the solvent from the obtained mixture through reduced pressure distillation, and washing and purifying with methanol and acetone to obtain a crude product; and dissolving the crude product in acetonitrile and toluene for recrystallization to obtain a black crystal which is a high-purity gold and silver nanocluster. 0.25g of high-purity gold and silver nanoclusters are taken and dispersed into 200ml of ethanol to obtain impregnation liquid containing the gold and silver nanoclusters; weighing 49.75g of active carbon and soaking the active carbon in impregnation liquid containing gold and silver nanoclusters; and centrifuging, filtering and drying the soaked activated carbon to finally obtain the gold and silver nanocluster catalyst.
Example 6 catalyst preparation
Weighing 1.28g of chloroauric acid and 715.33mg of silver nitrate, sequentially dissolving in 2261ml of acetonitrile, adding 11.66g of tetrabutylammonium bromide, adding 3.15g of adamantane thiol serving as a reducing agent and a gold stabilizing agent of high-valence gold while stirring, adding 10ml of sodium borohydride containing 13.29g into the solution when the solution is changed from deep red to be transparent, continuously stirring for 6 days, removing the solvent from the obtained mixture through reduced pressure distillation, and washing and purifying the mixture by using methanol and acetone to obtain a crude product; and dissolving the crude product in acetonitrile and toluene for recrystallization to obtain a black crystal which is a high-purity gold and silver nanocluster. Dispersing 0.75g of high-purity gold and silver nanoclusters into 200ml of acetone to obtain impregnation liquid containing the gold and silver nanoclusters; weighing 49.25g of active carbon, and soaking the active carbon in immersion liquid containing gold and silver nanoclusters; and centrifuging, filtering and drying the soaked activated carbon to finally obtain the gold and silver nanocluster catalyst.
EXAMPLE 7 hydrochlorination of acetylene
The catalysts prepared in examples 1 to 6 were used for the hydrochlorination of acetylene, respectively, as follows: reacting raw material gas C2H2And HCl (C)2H2And HCl in a molar ratio of 1: 1.08) is introduced into a fixed bed reactor filled with catalyst, the dosage of the catalyst is 3.0g, the temperature of a bed layer is controlled to be 180 ℃, and the space velocity of acetylene is 108h-1The reaction pressure was 0.02 MP.
The evaluation test results of the catalyst of the invention in the hydrochlorination reaction of acetylene are as follows: in examples 1 to 6, the selectivity of vinyl chloride was maintained at 99% or more; the activity comparison of the catalysts is presented as the acetylene conversion at which the catalyst reaches steady state, as shown in table 1.
Stability experiments were conducted with the catalyst prepared in example 1, the catalyst achieved vinyl chloride selectivity of 99.5% in the hydrochlorination of acetylene, and after 1600h of reaction, the conversion of acetylene is shown in fig. 1, and the selectivity of vinyl chloride in the reaction was maintained at 99% or more.
TABLE 1 results of the reactions of examples 1-6
Claims (8)
1. The catalyst takes gold-silver nanoclusters as an active component and takes a carbon material as a carrier;
the chemical formula of the gold and silver nanocluster is [ Au ]23@xAgx(S-Adm)15]Wherein x is 4-7; the structure of the gold and silver nanocluster is that a 24-face core consisting of gold and silver atoms covers three Au3(SR)4Structure and an AgS3Structure; in the chemical formula, S-Adm refers to adamantane thiol; SR refers to a thiol ligand.
2. The application of claim 1, wherein the loading amount of the gold and silver nanoclusters is 0.1-3 wt%; the carbon material is activated carbon; the gold and silver nanoclusters have positive valence metal properties.
3. Use according to claim 1, wherein the catalyst is prepared by:
1) dissolving a gold precursor and a silver precursor in a solvent I to obtain a solution I;
2) adding a surfactant into the solution I, and adding a thiol compound while stirring to obtain a dark red solution II;
3) when the solution II is changed from deep red to transparent, adding a reducing agent aqueous solution into the solution II, and continuously stirring for 1-7 days to obtain a solution III;
4) removing the solvent from the solution III by reduced pressure distillation to obtain a crude product, and washing and purifying the crude product by using methanol and acetone;
5) recrystallizing the purified crude product to obtain black crystals, wherein the black crystals are gold and silver nanoclusters;
6) and loading the gold and silver nanoclusters on activated carbon by an impregnation method.
4. Use according to claim 3, characterized in that said step 6) comprises the following steps:
I. purifying and dispersing the gold and silver nanoclusters into a solvent II to obtain a system I;
II. Adding activated carbon into the system I, and soaking at room temperature;
and III, centrifuging, filtering and drying the impregnated activated carbon to obtain the gold and silver nanocluster catalyst.
5. Use according to claim 3, wherein the gold precursor is chloroauric acid; the silver precursor is silver nitrate; the molar ratio of the gold precursor to the silver precursor is 1: 1-1: 2; the surfactant is one or more of tetrabutylammonium bromide, tetraoctylammonium bromide and tetraethylammonium bromide; the solvent I is a mixed solvent formed by one or more of diethyl ether, acetone, toluene, acetonitrile, methanol, ethanol and dimethyl sulfoxide; the reducing agent is one or more of lithium aluminum hydride, sodium borohydride, potassium borohydride and elementary iodine; the thiol compound is an aromatic or aliphatic compound containing sulfydryl; the number of carbons of the thiol compound is 8-12.
6. The use according to claim 5, wherein the thiol compound is one or more of octanethiol, nonanethiol, 1-decanethiol, 1-undecanethiol, and adamantanethiol.
7. The use according to claim 3, wherein the solvent II is one or more of ethanol, dichloromethane, dichloroethane, chloroform, acetone.
8. Use according to claim 1, characterized in that the reaction is carried out in a fixed bed reactor; the ratio of acetylene to hydrogen chloride is 1: 1-1: 1.08; the reaction temperature is 150-180 ℃; the reaction pressure is 0.01-0.1 MP; the space velocity of acetylene is 30-200 h-1The dosage of the catalyst is 3.0-6.0 g.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266784A (en) * | 2011-06-07 | 2011-12-07 | 李伟 | Preparation method for and application of novel load type composite metal catalyst |
| WO2012084643A2 (en) * | 2010-12-22 | 2012-06-28 | Solvay Sa | Catalytic system and its use for the manufacture of vinyl chloride by hydrochlorination of acetylene |
| 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 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012084643A2 (en) * | 2010-12-22 | 2012-06-28 | Solvay Sa | Catalytic system and its use for the manufacture of vinyl chloride by hydrochlorination of acetylene |
| CN102266784A (en) * | 2011-06-07 | 2011-12-07 | 李伟 | Preparation method for and application of novel load type composite metal catalyst |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| Structure of the Au23-xAgx(S-Adm)15 Nanocluster and Its Application for Photocatalytic Degradation of Organic Pollutants;Chao Liu et al.;《Angew. Chem. Int. Ed.》;20190703;第58卷;第11335-11339页 * |
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