A non-noble metal composite catalyst, a preparation method and application thereof

Abstract

The present application provides a non-noble metal composite catalyst, a preparation method and application thereof. Specifically, the present application provides a non-noble metal composite catalyst, which is prepared by impregnating a catalyst carrier in a metal salt solution, a cocatalytic metal salt solution (including an alkali metal salt solution or a rare earth metal salt solution), and a coordination compound solution.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalyst preparation and application, in particular, the present application relates to a non-noble metal composite catalyst and its preparation method and application BACKGROUND

[0002] Acetylene addition reaction is a very classic and important basic organic reaction. For example, acetylene and hydrogen chloride addition (acetylene hydrochlorination reaction) to synthesize vinyl chloride, vinyl acetylene hydrochlorination reaction to synthesize chlorobutadiene, acetylene hydration addition rearrangement to generate acetaldehyde, acetylene and acetic acid addition to generate vinyl acetate, and acetylene and carbon tetrachloride addition to generate tetrachloropropene. These reactions generate very important bulk chemical raw materials. The main catalysts used in the industrialization of acetylene addition reaction are mercury chloride, mercury sulfate, which have good effect but high toxicity. In order to avoid the damage of catalyst to the environment, non-mercury catalysts are widely researched in the industry. Non-mercury catalysts mainly include noble metal-based catalysts and non-noble metal-based catalysts. The former has high catalytic activity, but due to the use of gold or palladium, the cost is very high, which cannot meet the industrialization requirements of bulk chemical products. The latter non-noble metal catalysts mainly include copper, tin, bismuth, titanium and zinc, etc. The catalytic activity of this kind of catalyst is not ideal, and it is difficult to meet the requirements of industrial application. From the reaction mechanism, the catalytic activity of this kind of catalyst has a great relationship with the standard electrode potential of the element. According to the previous research reports, the catalytic activity and the standard electrode potential of the element are positively correlated, but the electrode potential of the non-noble metal element is not high, which cannot realize the high activity characteristics of single element or single composition, and cannot meet the industrial use, so it has been in the experimental research stage. Chinese patents CN 103007972 A, CN 103272619 A, CN 105126878 B, CN 102069000 A, CN 102430418 A, CN 101670293 A, CN 101497046 A, CN 109529893 A, CN 105330512 A, CN 102125830 B, CN 102698806 B reported a lot of research on non-noble metal catalysts, including catalyst additives, coordination molecule screening, and to a certain extent, improving the stability of the catalyst, but the catalytic activity of the catalyst is very limited.

[0003] The following are three fields of current active application research of acetylene addition reaction.(1) Chloroethylene is a very important chemical raw material, mainly used for the production of polyvinyl chloride resin (PVC), which is one of the world's five engineering plastics and has a very wide application in industrial and agricultural production. By 2016, the world's PVC production reached 40 million tons, China is the world's largest PVC producer, with an output of 25 million tons, and the market demand is growing at a rate of 5% per year. The current industrialized chloroethylene monomer production technology has acetylene hydrochlorination process and ethylene oxychlorination process. The acetylene hydrochlorination process is simple and mature, but the mercury chloride catalyst used in the reaction is easy to sublimate and lose, and it is serious pollution to the environment. To solve the problem of mercury catalyst pollution, research the development of catalysts to low-mercury and mercury-free, control and gradually eliminate mercury pollution, which is the most difficult task facing China's chlor-alkali chemical industry.(2) Polychoroprene rubber (Neoprene Rubber, CR) is the first synthetic rubber product to be industrialized in the industry, which is an organic high molecular chlorinated synthetic resin developed by DuPont Company in the 1980s, and then gradually entered the market. In the production process of chlorobutadiene rubber, the cost of butadiene method is higher than that of calcium carbide acetylene method, and the acetylene method for producing chlorobutadiene is more mature, but the acetylene method consumes more electricity. In addition, China's energy structure is rich in coal, poor in oil and gas, and with the maturation of the technology of acetylene production by calcium carbide method in recent years, the acetylene method for preparing chlorobutadiene has greater energy advantage in China.(3) HFO-1234yf is a new type of environmentally friendly refrigerant, which has excellent environmental parameters. In the face of increasingly stringent environmental protection today, low-toxicity, environmentally friendly and non-flammable HFO-1234yf as the most potential refrigerant will replace traditional CFCs refrigerants. Acetylene and carbon tetrachloride are added to synthesize 1,1,1,3-tetrachloropropene, which is then fluorinated and reformed to form the final product HFO-1234yf. There have been reports of using mercury chloride and palladium chloride catalysts, the former has serious environmental pollution, and the latter has high cost. Patent CN202010424459.X proposes a liquid phase conversion method, although the reaction temperature is reduced, but the reaction efficiency of liquid phase method is lower than that of gas-solid method.

[0004] In summary, there is an urgent need to develop a non-noble metal catalyst with high stability and good reaction activity in the field of acetylene addition reaction. SUMMARY

[0005] There is an urgent need to develop a catalyst with high stability and good reaction activity in the field.

[0006] In the first aspect of the present application, a non-noble metal composite catalyst is provided, which is prepared by the following steps:

[0007] (1) pretreating a catalyst carrier with a strong acid solution to obtain a pretreated catalyst carrier;

[0008] (2) modifying the catalyst carrier treated in step (1) to obtain a catalyst carrier with modified surface groups;

[0009] (3) providing a solution of a catalytically active component metal salt, a solution of a promoter metal salt (including a solution of an alkali metal salt or a solution of a rare earth metal salt), and a solution of a complexing compound;

[0010] (4) mixing the catalyst carrier with modified surface groups in step (2) with each solution obtained in step (3) to obtain an impregnated sample;

[0011] (5) drying and calcining the impregnated sample obtained in step (4) to obtain a non-noble metal composite catalyst for catalyzing addition reactions of alkynes.

[0012] In another preferred embodiment, the catalyst carrier is selected from the group consisting of activated carbon, alumina, silica, silicon carbide, and molecular sieves.

[0013] In another preferred embodiment, in step (1), the strong acid is selected from the group consisting of hydrochloric acid, nitric acid, and sulfuric acid; preferably, the concentration of the strong acid solution is 1-3 mol / L.

[0014] In another preferred embodiment, in step (1), the pretreatment includes impregnating with the strong acid solution at 30-100°C for 1-24 hours.

[0015] In another preferred embodiment, the pretreatment temperature is 50-80°C.

[0016] In another preferred embodiment, the pretreatment time is 5-10 hours.

[0017] In another preferred embodiment, after the pretreatment, the method further comprises washing with deionized water to neutral pH and drying at 50-150°C for standby use.

[0018] In another preferred embodiment, the drying temperature is 80-120°C.

[0019] In another preferred embodiment, in step (2), the modification treatment includes modifying the carrier with a precursor selected from the group consisting of an oxygen-containing precursor, a nitrogen-containing precursor, a sulfur-containing precursor, a phosphorus-containing precursor, and a boron-containing precursor.

[0020] In another preferred embodiment, the oxygen-containing precursor is selected from the group consisting of a C1-C10 alcohol reagent, a C1-C10 aldehyde reagent, a C1-C10 acid reagent, a C1-C10 ester reagent, or a combination thereof.

[0021] In another preferred embodiment, the oxygen-containing precursor is selected from the group consisting of nitric acid, ethylene glycol, furfural, acetic acid, citric acid, ethyl acetate, or a combination thereof.

[0022] In another preferred embodiment, the nitrogen-containing precursor is selected from the group consisting of ammonia, ammonium salt, nitric acid, C1-C10 amine, C1-C10 nitro compound.

[0023] In another preferred embodiment, the nitrogen-containing precursor is selected from the group consisting of ammonia, ammonium chloride, nitric acid, acrylamide, uric acid, imidazole, pyridine, pyrrole, lactam.

[0024] In another preferred embodiment, the sulfur-containing precursor is selected from the group consisting of sulfuric acid, sulfate, C1-C10 mercapto compound, C1-C10 thiourea compound.

[0025] In another preferred embodiment, the phosphorus-containing compound is selected from the group consisting of phosphoric acid, phosphate, organophosphorus compound, triphenylphosphine, diethylphosphine.

[0026] In another preferred embodiment, the boron-containing precursor is selected from the group consisting of boric acid, borax, organoboron compound.

[0027] In another preferred embodiment, in the modification treatment of step (2), the oxygen atom in the oxygen-containing precursor and the mass of the carrier are in the ratio of 1:0.1-10, preferably 1:0.1-0.3; and / or;

[0028] the nitrogen atom in the nitrogen-containing precursor and the mass of the carrier are in the ratio of 1:0.1-10, preferably 1:0.3-0.8; and / or;

[0029] the sulfur atom in the sulfur-containing precursor and the mass of the carrier are in the ratio of 1:0.1-10, preferably 1:0.8-3; and / or;

[0030] the phosphorus atom in the phosphorus-containing precursor and the mass of the carrier are in the ratio of 1:0.1-10, preferably 1:3-5; and / or;

[0031] the boron atom in the boron-containing precursor and the mass of the carrier are in the ratio of 1:0.1-10, preferably 1:5-10.

[0032] In another preferred embodiment, in step (2), the modification of the carrier is carried out under the assistance of ultrasonic waves, and the frequency of the ultrasonic waves is 20-100 KHZ.

[0033] In another preferred embodiment, the ultrasonic time is 0.1-10 hours.

[0034] In another preferred embodiment, the ultrasonic time is 0.1-10 hours.

[0035] In another preferred embodiment, in the step (2), the method further comprises drying the support after the ultrasonic treatment at 50-150°C.

[0036] In another preferred embodiment, in the step (2), the method further comprises calcining the dried support at 500-1000°C to obtain the surface-modified support.

[0037] In another preferred embodiment, the calcining time is 1-3 hours.

[0038] In another preferred embodiment, in the step (3), the metal salt of the catalytically active component is selected from the group consisting of MnCl3, TiCl3, PbCl4, CeCl4, IrCl3, PuCl5, CuCl2, CuCl, BiCl3, TiCl4, VCl4, or a combination thereof.

[0039] In another preferred embodiment, the metal salt of the catalytically active component comprises at least two components selected from the group consisting of MnCl3, TiCl3, PbCl4, CeCl4, IrCl3, PuCl5, CuCl2, CuCl, BiCl3, TiCl4, VCl4, or a combination thereof. In another preferred embodiment, the mass ratio of the total mass of the metal salt of the catalytically active component to the mass of the support is 1:0.1-50.

[0040] In another preferred embodiment, in the step (3), the metal salt of the promoter is selected from the group consisting of LiCl, KCl, NaCl, RbCl, CsCl, BaCl2, CaCl2, SrCl2, MgCl2, LaCl3, CeCl3, PrCl3, EuCl3, or a combination thereof.

[0041] In another preferred embodiment, the mass ratio of the metal salt of the promoter to the mass of the support is 1:0.1-100.

[0042] In another preferred embodiment, in the step (3), the complexing compound is selected from the group consisting of phosphorus-containing complexing compounds (such as H3PO4, triethyl phosphite, butyl phosphite, triphenyl phosphine, or a combination thereof), sulfur-containing complexing compounds (such as thiourea, ammonium persulfate, sodium persulfate, potassium thiocyanate, or a combination thereof), nitrogen-containing complexing compounds (such as ammonium chloride, methyl pyrrolidone, N,N-diethylacetamide, 1,10-phenanthroline), or a combination thereof.

[0043] In another preferred embodiment, the mass ratio of the complexing compound to the mass of the support is 1:0.1-50.

[0044] In another preferred embodiment, in the step (4), the impregnation comprises vacuum impregnation, preferably, the vacuum impregnation time is 0.1-10 hours.

[0045] In another preferred embodiment, in step (4), the immersing comprises ultrasonic-assisted immersing, preferably, the ultrasonic frequency is 20-100 KHZ.

[0046] In another preferred embodiment, in step (4), the ultrasonic time is 0.1-10 hours.

[0047] In another preferred embodiment, in step (5), the method further comprises drying the rotary-evaporated sample at 50-150℃.

[0048] In a second aspect of the present application, a method for catalytic addition of alkyne is provided, which comprises using the catalyst as described in any one of the first aspect of the present application as catalyst, and reacting alkyne with halide.

[0049] In another preferred embodiment, the alkyne is selected from the group consisting of vinylacetylene, acetylene, or a combination thereof.

[0050] In another preferred embodiment, the halide is selected from the group consisting of hydrogen chloride, carbon tetrachloride, or a combination thereof.

[0051] In another preferred embodiment, in the method, the molar ratio of acetylene to hydrogen chloride is 1:1-1.5.

[0052] In another preferred embodiment, in the method, the volume space velocity (calculated based on acetylene) of the acetylene hydrochlorination reaction is 10-150 h -1 .

[0053] In another preferred embodiment, in the method, the acetylene hydrochlorination reaction pressure is 0-1 MPa.

[0054] In another preferred embodiment, in the method, the acetylene hydrochlorination reaction temperature is 80-180℃.

[0055] In another preferred embodiment, the method comprises loading the catalyst as described in the first aspect of the present application into a fixed-bed reaction tube, and passing the first raw material and the second raw material through the reaction tube, so as to carry out the reaction.

[0056] In another preferred embodiment, the alkyne is vinylacetylene, and the halide is hydrogen chloride.

[0057] In another preferred embodiment, in the method, the molar ratio of vinylacetylene to hydrogen chloride is 1:1-1.5.

[0058] In another preferred embodiment, in the method, the volume space velocity (calculated based on vinylacetylene) of the vinylacetylene and hydrogen chloride reaction is 10-150 h -1 .

[0059] In another preferred embodiment, the reaction pressure is 0-1 MPa.

[0060] In another preferred embodiment, the reaction temperature is 80-180℃.

[0061] In another preferred embodiment, the alkyne is ethyne, and the halogenated hydrocarbon is carbon tetrachloride.

[0062] In another preferred embodiment, the molar ratio of ethyne to carbon tetrachloride raw materials is 1:(1-1.5).

[0063] In another preferred embodiment, the volume space velocity (calculated based on ethyne) of raw materials in the reaction of ethyne and carbon tetrachloride is 10-150 h-1. -1 .

[0064] In another preferred embodiment, the reaction pressure is 0-1 MPa.

[0065] In another preferred embodiment, the reaction temperature is 80-200℃.

[0066] It should be understood that, within the scope of the present application, each of the above technical features of the present application and each of the technical features specifically described below (such as in the examples) can be combined with each other to form new or preferred technical solutions. Due to the limited space, they will not be listed one by one here. BRIEF DESCRIPTION OF DRAWINGS

[0067] Figure 1 A process flow chart for the catalyst of the present application. DETAILED DESCRIPTION

[0068] The present application provides a non-noble metal composite catalyst for alkyne addition reaction, as well as a preparation method and application. The catalyst provided by the present application has high catalytic activity, good stability, is environmentally friendly, and has low production cost. Based on the above findings, the inventors have completed the present application.

[0069] Non-noble metal composite catalyst for alkyne addition reaction

[0070] In the past patents and documents, the selection of ligand additives mainly focuses on copper, bismuth, tin, cadmium, titanium, barium and other elements as the main active components, which lacks innovation in the selection of active components, so the catalytic activity does not show significant improvement. According to the catalytic reaction mechanism of ethyne hydrochlorination, the intermediate complex C2H2-MCl xThe more stable, the higher the catalytic activity of the catalyst, and the higher the selectivity of the product vinyl chloride. As an electron-donating molecule, acetylene has a high electron cloud density around it, and is easily adsorbed and activated by ions or molecules with a high standard potential potential, in other words, metal ions with a high standard potential potential have a high catalytic activity for acetylene hydrochlorination. According to this principle, a large number of non-noble metal compounds with a high standard potential potential are screened as active components of the catalyst for evaluation and verification, and the evaluation results show that metal compounds with a high standard potential potential have a high catalytic activity, and on this basis, a high-activity non-mercury catalyst is obtained.

[0071] The non-noble metal composite catalyst of the present application is prepared by the following method:

[0072] (1) The catalyst carrier is pretreated under certain conditions to obtain a pretreated catalyst carrier;

[0073] (2) The catalyst carrier treated in step (1) is modified under certain conditions to control the surface groups of the carrier and improve the dispersion and fixation of the catalytically active components;

[0074] (3) The catalytically active component metal salt solution, the cocatalyst metal salt solution, the alkali metal salt solution, the rare earth metal salt solution, and the coordination compound solution are prepared in sequence;

[0075] (4) The modified catalyst carrier in step (2) is mixed and impregnated with each of the solutions obtained in step (3);

[0076] (5) The impregnated sample is dried and calcined to obtain a non-mercury catalyst for catalyzing acetylene hydrochlorination.

[0077] In the above method, step (1) preferably further includes any one or more of the following features:

[0078] The catalyst carrier is selected from activated carbon, alumina, silicon oxide, silicon carbide, and molecular sieves;

[0079] The catalyst carrier can be pretreated with 2N hydrochloric acid solution, 2N nitric acid solution, or 2N sulfuric acid solution at 30-100℃ for 1-24 hours, washed with deionized water to neutral pH, and dried at 50-150℃ for standby. Further preferably, the pretreatment temperature is 50-80℃, further preferably the pretreatment time is 5-10 hours, and further preferably the drying temperature is 80-120℃.

[0080] Preferably, step (2) above further includes any one or more of the following features:

[0081] The surface modification of the carrier in step (2) includes modification with oxygen, nitrogen, sulfur, phosphorus and boron atoms. Oxygen-containing precursors mainly include alcohols, aldehydes, acids, esters and other compounds, including but not limited to nitric acid, ethylene glycol, furfural, acetic acid, citric acid, ethyl acetate. Nitrogen-containing precursors mainly include amine, amino, nitro and other compounds, including but not limited to ammonia, ammonium chloride, nitric acid, acrylamide, uric acid, imidazole, pyridine, pyrrole, lactam.

[0082] The modification agent precursor compound in step (2) can be one or more for carrier modification, and the amount of modification agent is 1:0.1-10 by mass ratio of oxygen, nitrogen, sulfur, phosphorus or boron atoms to the carrier, such as 1:0.1-0.3, 1:0.3-0.8, 1:0.8-3, 1:3-5, 1:5-10.

[0083] The carrier modification in step (2) is preferably carried out under the assistance of ultrasonic waves, and the ultrasonic frequency is 20-100 KHZ, such as 20-40 KHZ, 40-60 KHZ, 60-80 KHZ, 80-100 KHZ. The ultrasonic time is 0.1-10 hours, such as 0.1-2 hours, 2-4 hours, 4-6 hours, 6-8 hours, 8-10 hours.

[0084] Preferably, the step (2) further comprises: drying the carrier after ultrasonic treatment at 50-150°C, such as 50-70°C, 70-100°C, 100-120°C, 120-150°C; and calcining at 500-1000°C for 2 hours after drying, such as 500-600°C, 600-700°C, 700-800°C, 800-900°C, 900-1000°C.

[0085] In another preferred embodiment, the step (3) further comprises one or more of the following:

[0086] The non-noble metal catalytically active component in step (3) mainly includes metal salts with high standard potential, including but not limited to one or more of MnCl3, TiCl3, PbCl4, CeCl4, IrCl3, PuCl5, CuCl2, CuCl, BiCl3, TiCl4, VCl4; the total mass of the active component to the mass of the carrier is in the range of 1:(0.1-50), such as 1:(0.1-1), 1:(1-5), 1:(5-10), 1:(10-20), 1:(20-30), 1:(30-40), 1:(40-50).

[0087] In step (3), the alkali metal additives and rare earth metal additives mainly include, but are not limited to, LiCl, KCl, NaCl, RbCl, CsCl, BaCl2, CaCl2, SrCl2, MgCl2, LaCl3, CeCl3, PrCl3, EuCl3; the mass ratio of alkali metal additives to carrier is 1:(0.1~100), such as 1:(0.1~1), 1:(1~5), 1:(5-10), 1:(10~20), 1:(20~30), 1:(30~40), 1:(40~50), 1:(50~60), 1:(60~70), 1:(70~80), 1:(80~90), 1:(90~100).

[0088] The coordination compounds in step (3) mainly include, but are not limited to, phosphorus-containing compounds: H3PO4, triethyl phosphite, butyl phosphite, triphenylphosphite; sulfur-containing compounds: thiourea, ammonium persulfate, sodium persulfate, potassium thiocyanate; and nitrogen-containing compounds: ammonium chloride, methylpyrrolidone, N,N-diethylacetamide, 1,10-o-phenegrin. The mass ratio of coordination compound to support is 1:(0.1-50), such as 1:(0.1-1), 1:(1-5), 1:(5-10), 1:(10-20), 1:(20-30), 1:(30-40), 1:(40-50).

[0089] In another preferred embodiment, step (4) includes one or more of the following features:

[0090] In step (4), the modified carrier is impregnated in the solution obtained in step (3) and first subjected to vacuum impregnation for 0.1 to 10 hours, such as 0.1 to 1 hour, 1 to 2 hours, 2 to 3 hours, 3 to 4 hours, 4 to 5 hours, 5 to 6 hours, 6 to 7 hours, 7 to 8 hours, 8 to 9 hours, and 9 to 10 hours.

[0091] After vacuum impregnation in step (4), ultrasonic-assisted impregnation is performed at a frequency of 20–100 kHz, such as 20–40 kHz, 40–60 kHz, 60–80 kHz, or 80–100 kHz. The ultrasonic duration is 0.1–10 hours, such as 0.1–2 hours, 2–4 hours, 4–6 hours, 6–8 hours, or 8–10 hours. After ultrasonic impregnation, excess moisture is removed by rotary evaporation pre-drying.

[0092] In another preferred embodiment, step (5) includes one or more of the following features:

[0093] In step (5), the rotary evaporated sample is dried at 50-150°C, such as 50-70°C, 70-100°C, 100-120°C, 120-150°C; and then calcined at 500-1000°C for 2 hours, such as 500-600°C, 600-700°C, 700-800°C, 800-900°C, 900-1000°C.

[0094] Addition reaction of alkyne using non-noble metal composite catalyst

[0095] The non-noble metal composite catalyst prepared in the present application can be used in addition reaction of alkyne, such as addition reaction of alkyne and halogenated hydrocarbon, such as ethyne hydrochlorination reaction, vinyl acetylene hydrochlorination reaction, or addition reaction of ethyne and carbon tetrachloride.

[0096] When used in ethyne hydrochlorination addition reaction, the catalyst is loaded into a fixed bed reaction tube, and hydrogen chloride and ethyne are introduced for reaction. Preferably, the method further comprises one or more of the following features:

[0097] The molar ratio of ethyne to hydrogen chloride raw material is 1:(1-1.5), such as 1:(1-1.05), 1:(1.05-1.1), 1:(1.1-1.15), 1:(1.15-1.2), 1:(1.2-1.25), 1:(1.25-1.35), 1:(1.35-1.45), 1:(1.45-1.5).

[0098] In the ethyne hydrochlorination reaction, the volume space velocity (calculated based on ethyne) is 10-150h -1 , such as 10-20h -1 , 20-40h -1 , 40-60h -1 , 60-80h -1 , 80-90h -1 , 90-100h -1 , 100-120h -1 , 120-150h -1 .

[0099] The ethyne hydrochlorination reaction pressure is 0-1 MPa, such as 0-0.05 MPa, 0.05-0.1 MPa, 0.1-0.15 MPa, 0.15-0.2 MPa, 0.2-0.3 MPa, 0.3-0.4 MPa, 0.4-0.5 MPa, 0.5-0.6 MPa, 0.6-0.7 MPa, 0.7-0.8 MPa, 0.8-0.9 MPa, 0.9-1.0 MPa.

[0100] The acetylene hydrochlorination reaction temperature is preferably 80-180°C, such as 80-100°C, 100-120°C, 120-140°C, 140-160°C, 160-180°C.

[0101] The reaction product obtained after the hydrochlorination reaction is cooled, compressed, frozen, separated, and distilled to obtain vinyl chloride monomer.

[0102] When used for the addition reaction of vinyl acetylene and hydrogen chloride, the catalyst is packed into a fixed bed reaction tube and vinyl acetylene and hydrogen chloride are introduced to react. Preferably, the method further comprises one or more of the following features:

[0103] 1) The molar ratio of vinyl acetylene to hydrogen chloride raw material is 1:(1-1.5), such as 1:(1-1.05), 1:(1.05-1.1), 1:(1.1-1.15), 1:(1.15-1.2), 1:(1.2-1.25), 1:(1.25-1.35), 1:(1.35-1.45), 1:(1.45-1.5).

[0104] 2) The volume space velocity (based on vinyl acetylene) of the reaction of vinyl acetylene and hydrogen chloride is 10-150h -1 , such as 10-20h -1 , 20-40h -1 , 40-60h -1 , 60-80h -1 , 80-90h -1 , 90-100h -1 , 100-120h -1 , 120-150h -1 ;

[0105] 3) The reaction pressure is 0-1 MPa, such as 0-0.05 MPa, 0.05-0.1 MPa, 0.1-0.15 MPa, 0.15-0.2 MPa, 0.2-0.3 MPa, 0.3-0.4 MPa, 0.4-0.5 MPa, 0.5-0.6 MPa, 0.6-0.7 MPa, 0.7-0.8 MPa, 0.8-0.9 MPa, 0.9-1.0 MPa;

[0106] 4) The reaction temperature is 80-180°C, such as 80-100°C, 100-120°C, 120-140°C, 140-160°C, 160-180°C.

[0107] When used for the addition reaction of acetylene and carbon tetrachloride, the method comprises: packing the catalyst into a fixed bed reaction tube and introducing acetylene and carbon tetrachloride to react. Preferably, the method further comprises one or more of the following:

[0108] 1) the molar ratio of acetylene to carbon tetrachloride raw material is 1:(1-1.5), such as 1:(1-1.05), 1:(1.05-1.1), 1:(1.1-1.15), 1:(1.15-1.2), 1:(1.2-1.25), 1:(1.25-1.35), 1:(1.35-1.45), 1:(1.45-1.5).

[0109] 2) the volume space velocity (calculated by acetylene) of acetylene reacting with carbon tetrachloride is 10-150h -1 , such as 10-20h -1 , 20-40h -1 , 40-60h -1 , 60-80h -1 , 80-90h -1 , 90-100h -1 , 100-120h -1 , 120-150h -1 ;

[0110] 3) the reaction pressure is 0-1MPa, such as 0-0.05MPa, 0.05-0.1MPa, 0.1-0.15MPa, 0.15-0.2MPa, 0.2-0.3MPa, 0.3-0.4MPa, 0.4-0.5MPa, 0.5-0.6MPa, 0.6-0.7MPa, 0.7-0.8MPa, 0.8-0.9MPa, 0.9-1.0MPa;

[0111] 4) the reaction temperature is 80-200℃, such as 80-100℃, 100-120℃, 120-140℃, 140-160℃, 160-180℃, 180-200℃.

[0112] The present application discards the blindness in the preparation process of the traditional catalyst, focuses on the catalytic mechanism, scientifically screens and finds the catalytically active component compound, and the chemical action between different compounds, to form the overall synergistic catalytic effect. Based on such idea, we develop a high-activity catalyst in the present application, which can significantly improve the activity compared with the reported non-noble metal catalyst.

[0113] The present application is significant in developing a brand-new non-noble metal composite catalyst, which can completely replace the current mercury-activated coal catalyst for industrial production of chloroethylene, and can also be used in the hydrochlorination reaction of vinyl acetylene and the addition reaction of acetylene carbon tetrachloride, and will not cause damage to the environment, belonging to the environment-friendly catalyst.

[0114] Compared with the prior art, the technical effects of the present application mainly embody in:

[0115] 1) The present application is based on the reaction mechanism, a large number of non-noble metal salt with high standard electrode potential is screened, the synergistic effect of these metal ions shows the characteristics of noble metal salt, strongly adsorbs and activates acetylene molecules, and produces very high catalytic activity and stability, at 120℃, the initial single-pass conversion rate of acetylene can reach 95% under normal pressure, the selectivity of vinyl chloride is greater than 98%, and the catalyst can be used for ethylene-vinyl acetylene addition reaction and acetylene-carbon tetrachloride addition reaction. -1 , the initial single-pass conversion rate of acetylene can reach 95% under normal pressure, the selectivity of vinyl chloride is greater than 98%, and the catalyst can be used for ethylene-vinyl acetylene addition reaction and acetylene-carbon tetrachloride addition reaction.

[0116] 2) Since the standard electrode potential of non-noble metal and rare earth metal ions is negative, it can reflect the effect of stabilizing the catalyst; the addition of some coordination compound molecules improves the dispersion and fixation of the active component, reduces the loss during the reaction; in addition, the use of vacuum and ultrasonic assisted impregnation improves the dispersion and fixation of the active component and improves the stability of the catalyst.

[0117] 3) The present application uses non-noble metal as raw material, the cost is much lower than that of noble metal catalyst, and it is environmentally friendly.

[0118] The present application will be further described in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present application and not to limit the scope of the present application. The experimental methods in the following examples are not specified, which are usually carried out under conventional conditions or according to the conditions recommended by the manufacturer. Unless otherwise specified, percentages and parts are calculated by weight.

[0119] Preparation example

[0120] The following examples 1-9 relate to the preparation of non-noble metal composite catalyst, unless otherwise specified, the main implementation steps include:

[0121] (1) The catalyst carrier is pretreated under certain conditions to obtain a pretreated catalyst carrier;

[0122] (2) The catalyst carrier treated in step (1) is modified under certain conditions to control the surface groups of the carrier and improve the dispersion and fixation of the catalytically active component;

[0123] (3) The catalytically active component metal salt solution, the cocatalyst metal salt solution, the alkali metal salt solution, the rare earth metal salt solution and the coordination compound solution are prepared in turn;

[0124] (4) The modified catalyst carrier in step (2) is mixed and impregnated with each solution obtained in step (3);

[0125] (5) The impregnated sample is dried and calcined to obtain a non-mercury catalyst for catalyzing acetylene hydrochlorination reaction.

[0126] Example 1

[0127] (1) Take 10 g of 40 mesh activated carbon, pretreat with 2N hydrochloric acid solution at 60°C for 4 hours, then wash with deionized water to neutral pH, then dry at 100°C for 10 hours and reserve.

[0128] (2) The pretreated activated carbon is mixed with 2N nitric acid and ammonium chloride solution, the mass ratio of nitrogen atoms to activated carbon is controlled at 1:10, ultrasonic immersion is carried out at 50KHZ for 2 hours, after ultrasonic immersion, dry at 110°C for 12 hours, then place in a tube furnace, calcine under nitrogen atmosphere for 2 hours, to obtain modified activated carbon.

[0129] (3) Take a mixture of MnCl3 and PbCl4, control the mass ratio to activated carbon at 1:10, dissolve in water to obtain solution I; take an appropriate amount of LiCl and LaCl3, control the mass ratio to activated carbon at 1:20, dissolve in water to obtain solution II; take an appropriate amount of triethyl phosphite, control the mass ratio to activated carbon at 1:15, dissolve in water and ethanol to obtain solution III.

[0130] (4) Mix solutions I, II and III, then immerse the modified activated carbon, first vacuum immersion for 2 hours, then ultrasonic assisted immersion at 50KHZ for 3 hours, then remove water by rotary evaporation, to obtain a preliminary dried sample;

[0131] (5) Dry the preliminary dried sample at 120°C for 5 hours, then place in a 500°C tube furnace, calcine under nitrogen atmosphere for 2 hours to obtain non-mercury catalyst C1.

[0132] Example 2

[0133] (1) Take 10 g of 40 mesh activated carbon, pretreat with 2N nitric acid solution at 80°C for 3 hours, then wash with deionized water to neutral pH, then dry at 120°C for 5 hours and reserve;

[0134] (2) Mix the pretreated activated carbon with acrylamide and ammonium sulfate solution, control the mass ratio of nitrogen and sulfur atoms to activated carbon at 1:5, ultrasonic immersion at 70KHZ for 4 hours, after ultrasonic immersion, dry at 130°C for 8 hours, then place in a tube furnace, calcine under nitrogen atmosphere for 2 hours, to obtain modified activated carbon;

[0135] (3) Take a mixture of TiCl3 and IrCl3, control the mass ratio to activated carbon at 1:20, dissolve in water to obtain solution I; take an appropriate amount of BaCl2 and LaCl3, control the mass ratio to activated carbon at 1:30, dissolve in water to obtain solution II; take an appropriate amount of triphenylphosphine, control the mass ratio to activated carbon at 1:20, dissolve in water and ethanol to obtain solution III;

[0136] (4) After mixing the three solutions I, II and III, the modified activated carbon is added for impregnation. First, vacuum impregnation is performed for 4 hours, and then ultrasonic assistance at 50 KHZ is performed for 6 hours. Then, water is removed by rotary evaporation to obtain a preliminary dried sample;

[0137] (5) The preliminary dried sample is dried at 100°C for 10 hours, and then placed in a 500°C tube furnace under a nitrogen atmosphere for 2 hours to obtain a non-mercury catalyst C2.

[0138] Example 3

[0139] (1) 10g of activated carbon with a mesh size of 40 is weighed, pretreated with a 2N nitric acid solution at 60°C for 6 hours, then washed with deionized water until the pH is neutral, and then dried at 150°C for 4 hours for standby;

[0140] (2) The pretreated activated carbon is mixed with a urea and thiourea solution, with the mass ratio of nitrogen and sulfur atoms to activated carbon controlled at 1:10, ultrasonically impregnated at 60 KHZ for 4 hours, and then dried at 100°C for 12 hours after the ultrasonic impregnation is completed. Then, it is placed in a tube furnace and calcined under a nitrogen atmosphere for 2 hours to obtain a modified activated carbon;

[0141] (3) A mixture of CeCl4 and BiCl3 is weighed, with the mass ratio to activated carbon controlled at 1:10, and dissolved in water to obtain solution I. An appropriate amount of SrCl2 and EuCl3 is weighed, with the mass ratio to activated carbon controlled at 1:40, and dissolved in water to obtain solution II. An appropriate amount of potassium thiocyanate is weighed, with the mass ratio to activated carbon controlled at 1:20, and dissolved in water and ethanol to obtain solution III;

[0142] (4) After mixing the three solutions I, II and III, the modified activated carbon is added for impregnation. First, vacuum impregnation is performed for 3 hours, and then ultrasonic assistance at 60 KHZ is performed for 8 hours. Then, water is removed by rotary evaporation to obtain a preliminary dried sample;

[0143] (5) The preliminary dried sample is dried at 120°C for 8 hours, and then placed in a 550°C tube furnace under a nitrogen atmosphere for 2 hours to obtain a non-mercury catalyst C3.

[0144] Example 4

[0145] (1) 10g of activated carbon with a mesh size of 50 is weighed, pretreated with a 2N hydrochloric acid solution at 80°C for 5 hours, then washed with deionized water until the pH is neutral, and then dried at 120°C for 8 hours for standby;

[0146] (2) The pretreated activated carbon is mixed with phosphoric acid and sulfuric acid solution, the mass ratio of phosphorus and sulfur atoms to activated carbon is controlled at 1:8, ultrasonic immersion is performed at 60 KHZ for 5 hours, after the ultrasonic immersion is completed, drying is performed at 120°C for 6 hours, and then the modified activated carbon is placed in a tube furnace, calcined for 2 hours under a nitrogen atmosphere, and the modified activated carbon is obtained;

[0147] (3) A mixture of PuCl5 and CuCl2 is weighed, the mass ratio of the mixture to activated carbon is controlled at 1:15, water is added to dissolve to obtain solution I; an appropriate amount of CaCl2 and PrCl3 is weighed, the mass ratio of the mixture to activated carbon is controlled at 1:30, water is added to dissolve to obtain solution II; an appropriate amount of methyl pyrrolidone is weighed, the mass ratio of the mixture to activated carbon is controlled at 1:20, water and ethanol are added to dissolve to obtain solution III;

[0148] (4) The three solutions I, II and III are mixed, the modified activated carbon is added for immersion, vacuum immersion is performed for 2 hours, then ultrasonic wave assisted immersion is performed at 60 KHZ for 6 hours, and then water is removed by rotary evaporation to obtain a preliminarily dried sample;

[0149] (5) The preliminarily dried sample is dried at 120°C for 10 hours, and then placed in a 500°C tube furnace for calcination under a nitrogen atmosphere for 2 hours to obtain a non-mercury catalyst C4.

[0150] Example 5

[0151] (1) 10g of 50 mesh activated carbon is weighed, pretreated with 2N hydrochloric acid solution at 60°C for 10 hours, then washed with deionized water until the pH is neutral, then dried at 130°C for 5 hours, and then used;

[0152] (2) The pretreated activated carbon is mixed with ammonium hydrogen phosphate and borax solution, the mass ratio of phosphorus and boron atoms to activated carbon is controlled at 1:10, ultrasonic immersion is performed at 60 KHZ for 4 hours, after the ultrasonic immersion is completed, drying is performed at 150°C for 4 hours, and then the modified activated carbon is placed in a tube furnace, calcined for 2 hours under a nitrogen atmosphere, and the modified activated carbon is obtained;

[0153] (3) A mixture of CuCl2 and BiCl3 is weighed, the mass ratio of the mixture to activated carbon is controlled at 1:5, water is added to dissolve to obtain solution I; an appropriate amount of KCl and PrCl3 is weighed, the mass ratio of the mixture to activated carbon is controlled at 1:20, water is added to dissolve to obtain solution II; an appropriate amount of N-methyl lactam is weighed, the mass ratio of the mixture to activated carbon is controlled at 1:50, water and ethanol are added to dissolve to obtain solution III;

[0154] (4) The three solutions I, II and III are mixed, the modified activated carbon is added for immersion, vacuum immersion is performed for 4 hours, then ultrasonic wave assisted immersion is performed at 70 KHZ for 2 hours, and then water is removed by rotary evaporation to obtain a preliminarily dried sample;

[0155] (5) The preliminary dried sample is dried at 150°C for 5 hours, and then placed in a 550°C tube furnace under nitrogen atmosphere for 2 hours to obtain non-mercury catalyst C5.

[0156] Example 6

[0157] (1) 10 g of 50-mesh activated carbon is weighed, pretreated with 2N hydrochloric acid solution at 70°C for 8 hours, then washed with deionized water until neutral, and then dried at 110°C for 6 hours for standby;

[0158] (2) The pretreated activated carbon is mixed with a solution of ammonium hydrogen phosphate and borax, and the mass ratio of phosphorus and boron to activated carbon is controlled at 1:15, ultrasonic immersion is performed at 60KHZ for 5 hours, after the ultrasonic immersion is completed, drying is performed at 120°C for 6 hours, and then placed in a tube furnace, calcined under nitrogen atmosphere for 2 hours to obtain modified activated carbon;

[0159] (3) A mixture of BiCl3 and TiCl4 is weighed, and the mass ratio of the mixture to activated carbon is controlled at 1:8 to obtain solution I; an appropriate amount of CsCl and PrCl3 is weighed, and the mass ratio of the mixture to activated carbon is controlled at 1:15 to obtain solution II; an appropriate amount of N, N-diethylacetamide is weighed, and the mass ratio of the mixture to activated carbon is controlled at 1:30 to obtain solution III;

[0160] (4) The three solutions I, II and III are mixed, and the modified activated carbon is added for immersion, vacuum immersion is performed for 6 hours, and then ultrasonic assisted immersion is performed at 60KHZ for 2 hours, and then water is removed by rotary evaporation to obtain a preliminary dried sample;

[0161] (5) The preliminary dried sample is dried at 120°C for 6 hours, and then placed in a 600°C tube furnace under nitrogen atmosphere for 2 hours to obtain non-mercury catalyst C6.

[0162] Example 7

[0163] (1) 10 g of 40-mesh activated carbon is weighed, pretreated with 2N hydrochloric acid solution at 50°C for 10 hours, then washed with deionized water until neutral, and then dried at 140°C for 8 hours for standby;

[0164] (2) The pretreated activated carbon is mixed with a solution of pyridine and borax, and the mass ratio of nitrogen and boron to activated carbon is controlled at 1:10, ultrasonic immersion is performed at 60KHZ for 8 hours, after the ultrasonic immersion is completed, drying is performed at 80°C for 20 hours, and then placed in a tube furnace, calcined under nitrogen atmosphere for 2 hours to obtain modified activated carbon;

[0165] (3) CuCl2and TiCl4mixture is weighed, the mass ratio of CuCl2and TiCl4to activated carbon is controlled to be 1:10, and water is added to dissolve to obtain solution I; an appropriate amount of LiCl and LaCl3is weighed, the mass ratio of LiCl and LaCl3to activated carbon is controlled to be 1:20, and water is added to dissolve to obtain solution II; an appropriate amount of 1,10-phenanthroline is weighed, the mass ratio of 1,10-phenanthroline to activated carbon is controlled to be 1:20, and water and ethanol are added to dissolve to obtain solution III;

[0166] (4) After the three solutions I, II and III are mixed, the modified activated carbon is added for impregnation, vacuum impregnation is first performed for 3 hours, then ultrasonic wave assisted impregnation is performed for 2 hours under 70 KHZ, then water is removed by rotary evaporation to obtain a preliminarily dried sample;

[0167] (5) The preliminarily dried sample is dried at 150°C for 6 hours, and then is placed in a 500°C tube furnace under a nitrogen atmosphere to be burned for 2 hours to obtain a non-mercury catalyst C7.

[0168] Example 8

[0169] (1) 10 g of activated carbon with a mesh size of 40 is weighed, pretreated with a 2N hydrochloric acid solution at 60°C for 8 hours, then washed with deionized water until the pH is neutral, and then dried at 120°C for 6 hours for standby;

[0170] (2) The pretreated activated carbon is mixed with a pyridine and borax solution, the mass ratio of nitrogen and boron atoms to activated carbon is controlled to be 1:15, ultrasonic impregnation is performed at 60 KHZ for 6 hours, after the ultrasonic impregnation is completed, the sample is dried at 60°C for 20 hours, and then is placed in a tube furnace, burned for 2 hours under a nitrogen atmosphere to obtain modified activated carbon;

[0171] (3) A mixture of CuCl2, CeCl3and TiCl4is weighed, the mass ratio of CuCl2, CeCl3and TiCl4to activated carbon is controlled to be 1:12, and water is added to dissolve to obtain solution I; an appropriate amount of BaCl2and LaCl3is weighed, the mass ratio of BaCl2and LaCl3to activated carbon is controlled to be 1:25, and water is added to dissolve to obtain solution II; an appropriate amount of ammonium persulfate is weighed, the mass ratio of ammonium persulfate to activated carbon is controlled to be 1:15, and water and ethanol are added to dissolve to obtain solution III;

[0172] (4) After the three solutions I, II and III are mixed, the modified activated carbon is added for impregnation, vacuum impregnation is first performed for 5 hours, then ultrasonic wave assisted impregnation is performed for 4 hours under 70 KHZ, then water is removed by rotary evaporation to obtain a preliminarily dried sample;

[0173] (5) The preliminarily dried sample is dried at 120°C for 4 hours, and then is placed in a 500°C tube furnace under a nitrogen atmosphere to be burned for 2 hours to obtain a non-mercury catalyst C8.

[0174] Example 9

[0175] (1) Take 10 g of 40 mesh activated carbon, pretreat with 2N hydrochloric acid solution at 80°C for 6 hours, then wash with deionized water until neutral, then dry at 140°C for 4 hours and reserve;

[0176] (2) Mix the pretreated activated carbon with pyridine and borax solution, control the mass ratio of nitrogen and boron atoms to activated carbon at 1:20, ultrasonic immersion at 60KHZ for 6 hours, after ultrasonic immersion, dry at 80°C for 16 hours, then place in a tube furnace, calcine under nitrogen atmosphere for 2 hours, to obtain modified activated carbon;

[0177] (3) Take CuCl2, CeCl3, TiCl4 and VCl4 mixture, control the mass ratio to activated carbon at 1:10, dissolve in water to obtain solution I; take appropriate amount of KCl and LaCl3, control the mass ratio to activated carbon at 1:15, dissolve in water to obtain solution II; take appropriate amount of thiourea, control the mass ratio to activated carbon at 1:20, dissolve in water and ethanol to obtain solution III;

[0178] (4) Mix solutions I, II and III, then immerse the modified activated carbon, first vacuum immersion for 6 hours, then ultrasonic assisted immersion at 70KHZ for 6 hours, then remove water by rotary evaporation to obtain a preliminary dried sample;

[0179] (5) Dry the preliminary dried sample at 150°C for 4 hours, then place in a 550°C tube furnace under nitrogen atmosphere and calcine for 2 hours to obtain non-mercury catalyst C9.

[0180] Comparative Example 1

[0181] (1) Take 10 g of 40 mesh activated carbon, pretreat with 2N hydrochloric acid solution at 60°C for 6 hours, then wash with deionized water until neutral, then dry at 120°C for 5 hours and reserve;

[0182] (2) Mix the pretreated activated carbon with pyridine and borax solution, control the mass ratio of nitrogen and boron atoms to activated carbon at 1:15, ultrasonic immersion at 60KHZ for 8 hours, after ultrasonic immersion, dry at 60°C for 16 hours, then place in a tube furnace, calcine under nitrogen atmosphere for 2 hours, to obtain modified activated carbon;

[0183] (3) Take CuCl2, control the mass ratio to activated carbon at 1:10, dissolve in water to obtain solution I; take appropriate amount of KCl and LaCl3, control the mass ratio to activated carbon at 1:20, dissolve in water to obtain solution II; take appropriate amount of thiourea, control the mass ratio to activated carbon at 1:20, dissolve in water and ethanol to obtain solution III;

[0184] (4) After mixing the three solutions of I, II and III, the modified activated carbon is added for impregnation. First, vacuum impregnation is performed for 5 hours, and then ultrasonic assistance at 70 KHZ is performed for 4 hours. Then, water is removed by rotary evaporation to obtain a preliminary dried sample;

[0185] (5) The preliminary dried sample is dried at 120°C for 6 hours, and then placed in a 500°C tube furnace under a nitrogen atmosphere for 2 hours to obtain a non-mercury catalyst C10.

[0186] Test Examples

[0187] In this part, the C1-C10 non-noble metal composite catalyst prepared in the first part is used in the reaction for evaluation.

[0188] Test Example 1: Catalyzing the Hydrochlorination Reaction of Acetylene

[0189] Take 1 g of C1-C10 catalyst sample and load it into a reaction tube with a diameter of 10 mm. The catalyst activity and stability are evaluated in a fixed bed reactor. The molar ratio of acetylene to hydrogen chloride is 1: (1-1.5), the acetylene space velocity is 10-150 h -1 , the reaction temperature is 80-180°C, the reaction pressure is 0-1 MPa, and the gas phase products are analyzed by gas chromatography. The catalyst evaluation results are shown in Table 1 (in the table, the acetylene conversion rate is the initial highest conversion rate).

[0190] Table 1: Evaluation results of C1-C10 catalyst

[0191]

[0192]

[0193] Test Example 2: Catalyzing the Hydrochlorination Reaction of Vinyl Acetylene

[0194] Take 1 g of C1-C10 catalyst sample and load it into a reaction tube with a diameter of 10 mm. The catalyst activity and stability are evaluated in a fixed bed reactor. The molar ratio of vinyl acetylene to hydrogen chloride is 1: (1-1.5), the vinyl acetylene space velocity is 10-150 h -1 , the reaction temperature is 80-180°C, the reaction pressure is 0-1 MPa, and the gas phase products are analyzed by gas chromatography. The catalyst evaluation results are shown in Table 2 (in the table, the vinyl acetylene conversion rate is the initial highest conversion rate).

[0195] Table 2: Evaluation results of C1-C10 catalyst

[0196]

[0197] Test Example 3: Catalyzing the Carbon Tetrachloride Addition Reaction of Acetylene

[0198] Catalyst sample 1 g of C1-C10 was charged into a 10 mm diameter reaction tube, and the activity and stability of the catalyst were evaluated in a fixed bed reactor, acetylene and carbon tetrachloride molar ratio 1: (1-1.5), acetylene space velocity 10-150 h -1 , reaction temperature 80-250 °C, reaction pressure 0-1 MPa, and the gaseous products were analyzed by gas chromatography. The results of the catalyst evaluation are shown in Table 3 (acetylene conversion is the initial maximum conversion).

[0199] Table 3. Results of the evaluation of C1-C10 catalyst

[0200]

[0201] From the above Test Examples 1-3, it can be seen that the conversion of the product is significantly improved when catalysis is carried out using the catalyst of the present application. In particular, when two or three catalytically active component metal salts are used in conjunction, the catalytic activity is greatly improved.

[0202] All documents referred to in this disclosure are incorporated herein by reference as if each were individually incorporated by reference. In addition, it is to be understood that various modifications or alterations can be made to the above-disclosed teachings without departing from the scope of the present application. It is intended that all such modifications and alterations be considered as falling within the scope of the appended claims.

Claims

1. A non-precious metal composite catalyst, characterized in that, The catalyst is prepared by the following steps: (1) The catalyst support is pretreated with a strong acid solution to obtain the pretreated catalyst support; (2) The catalyst support after step (1) is modified to obtain a catalyst support with modified surface groups; (3) Provide catalytically active component metal salt solution, co-catalytic metal salt solution, and coordination compound solution; (4) The surface group modified catalyst support described in step (2) is mixed with the solutions obtained in step (3) and impregnated to obtain the impregnated sample; (5) The impregnated sample obtained in step (4) is dried and calcined to obtain a non-precious metal composite catalyst for catalyzing alkyne addition reaction; In step (1), the strong acid is selected from the following group: hydrochloric acid, nitric acid, and sulfuric acid; In step (1), the catalyst support is selected from the group consisting of activated carbon, alumina, silicon oxide, silicon carbide, and molecular sieves. The coordination compound is selected from the group consisting of: triethyl phosphite, butyl phosphite, triphenylphosphite, thiourea, potassium thiocyanate, methylpyrrolidone, N,N-diethylacetamide, 1,10-o-phenegrin, or combinations thereof; The co-catalytic metal salt is selected from the group consisting of: LiCl, KCl, NaCl, RbCl, CsCl, BaCl2, CaCl2, SrCl2, MgCl2, LaCl3, CeCl3, PrCl3, EuCl3, or combinations thereof; The total mass ratio of the catalytically active metal salt component to the support is 1:0.1-50; The mass ratio of the co-catalytic metal salt to the support is 1:0.1 to 100; The mass ratio of the coordination compound to the support is 1:0.1~50; The catalytically active metal salt comprises at least two components selected from the group consisting of: MnCl3, TiCl3, PbCl4, CeCl4, IrCl3, CuCl2, BiCl3, TiCl4, and VCl4.

2. The catalyst as described in claim 1, characterized in that, The catalytically active metal salt comprises at least two components selected from the group consisting of: TiCl3, CeCl4, CuCl2, and BiCl3.

3. The catalyst as described in claim 1, characterized in that, The catalyst support is activated carbon.

4. The catalyst as described in claim 1, characterized in that, In step (1), the pretreatment includes: immersion in a strong acid solution at 30-100 °C for 1-24 hours.

5. The catalyst as described in claim 1, characterized in that, In step (2), the modification treatment includes modifying the carrier with a precursor selected from the group consisting of oxygen-containing precursors, nitrogen-containing precursors, sulfur-containing precursors, phosphorus-containing precursors, and boron-containing precursors.

6. The catalyst as described in claim 5, characterized in that, The oxygen-containing precursor is selected from the group consisting of: C1-C10 alcohols, C1-C10 aldehydes, C1-C10 acids, C1-C10 esters, or combinations thereof. The nitrogen-containing precursor is selected from the group consisting of: ammonia, ammonium salts, nitric acid, C1-C10 amines, and C1-C10 nitro compounds. The sulfur-containing precursor is selected from the following group: sulfuric acid, sulfate, C1-C10 thiol compounds, and C1-C10 thiourea compounds; The phosphorus-containing precursor is selected from the group consisting of: phosphoric acid, phosphates, triphenylphosphine, diethylphosphine; and / or The boron-containing precursor is selected from the group consisting of boric acid, borax, and organoboron compounds.

7. The catalyst as described in claim 1, characterized in that, The catalytically active metal salt is selected from the following group: (1) MnCl3 and PbCl4; (2) TiCl3 and IrCl3; (3) CeCl4 and BiCl3; (4) CuCl2 and BiCl3; (5) TiCl4 and BiCl3; (6) CuCl2 and TiCl4; In step (3), the co-catalytic metal salt is selected from the following group: (1-1) LiCl and LaCl3; (2-1) BaCl2 and LaCl3; (3-1) SrCl2 and EuCl3; (4-1) CaCl2 and PrCl3; (5-1) KCl and PrCl3; (6-1) CsCl and PrCl3; (7-1) LiCl and LaCl3; (8-1) BaCl2 and LaCl3; (9-1) KCl and LaCl3.

8. A method for catalytic addition of alkynes, characterized in that, The preparation is carried out by reacting an alkyne with a halide using the catalyst described in any one of claims 1-7; wherein the alkyne is selected from the group consisting of vinylacetylene, acetylene, or combinations thereof. The halide is selected from the group consisting of hydrogen chloride, carbon tetrachloride, or combinations thereof.

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