A method for preparing vinyl chloride by reacting acetylene with hydrogen chloride

Abstract

This invention provides a method for preparing vinyl chloride from the reaction of acetylene and hydrogen chloride. Specifically, this invention provides a method for preparing vinyl chloride from acetylene and hydrogen chloride, the method comprising the following steps: loading a catalyst into a fixed-bed reaction tube, and allowing the acetylene and hydrogen chloride to pass through the reaction tube to react; wherein the catalyst is prepared by impregnating a catalyst support in a metal salt solution, a co-catalytic 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] This invention relates to the field of vinyl chloride, and specifically, it provides a method for preparing vinyl chloride by reacting acetylene with hydrogen chloride. Background Technology

[0002] Vinyl chloride is a very important chemical raw material, mainly used in the production of polyvinyl chloride resin (PVC). PVC is one of the world's five major engineering plastics and has a wide range of applications in industrial and agricultural production. Solving the problem of mercury catalyst pollution, researching catalysts towards low-mercury and mercury-free directions, and controlling and gradually eliminating mercury pollution are the most arduous tasks facing our chlor-alkali chemical industry.

[0003] Domestic and international scholars have conducted extensive research on mercury-free catalysts, reporting on both the active components and supports of these catalysts. Compared to the shortcomings of both noble metal and non-metal catalysts, non-noble metal catalysts show the greatest potential for development. While numerous research reports have been published on the development of mercury-free non-noble metal catalysts, they have yet to be truly industrialized. The main problem remains that the activity and stability of these catalysts do not meet industrial requirements, and their catalytic performance still lags behind that of mercuric chloride catalysts. Chinese patents CN 103007972 A, CN 103272619 A, CN 105126878 B, CN102069000 A, CN 102430418 A, CN 101670293A, CN 101497046A, CN 109529893 A, CN105330512 A, CN 102125830 B, and CN 102698806 B have reported a great deal of research on non-precious metal catalysts, covering the screening of catalyst promoters and coordination molecules. These studies have improved catalyst stability to some extent, but their improvement on catalyst catalytic activity is very limited.

[0004] In summary, there is an urgent need in this field to develop a catalyst with high stability and good reactivity suitable for the acetylene hydrochlorination reaction, as well as a corresponding acetylene hydrochlorination reaction method. Summary of the Invention

[0005] The purpose of this invention is to provide a catalyst with high stability and good reactivity suitable for the hydrochlorination of acetylene, as well as a corresponding method for the hydrochlorination of acetylene.

[0006] A first aspect of the present invention provides a method for preparing vinyl chloride from acetylene and hydrogen chloride, comprising the following steps:

[0007] A catalyst is loaded into a fixed-bed reaction tube, and the acetylene and hydrogen chloride are passed through the reaction tube to carry out the reaction; wherein the catalyst is prepared by the following method:

[0008] (1) The catalyst support is pretreated with a strong acid solution to obtain the pretreated catalyst support;

[0009] (2) The catalyst support after step (1) is modified to obtain a catalyst support with modified surface groups;

[0010] (3) Provide catalytically active component metal salt solution, co-catalytic metal salt solution (including alkali metal salt solution or rare earth metal salt solution), and coordination compound solution;

[0011] (4) The surface group modified catalyst support described in step (2) is mixed with each solution obtained in step (3) and impregnated to obtain the impregnated sample;

[0012] (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.

[0013] In another preferred embodiment, the molar ratio of acetylene to hydrogen chloride feedstock is 1:1 to 1.5.

[0014] In another preferred embodiment, the volume hourly space velocity (based on acetylene) for the acetylene hydrochlorination reaction is 10–150 h⁻¹. -1 .

[0015] In another preferred embodiment, the method is described at a acetylene hydrochlorination reaction pressure of 0-1 MPa.

[0016] In another preferred embodiment, the reaction temperature in the method is 80~180℃.

[0017] In another preferred embodiment, the catalyst support is selected from the group consisting of activated carbon, alumina, silicon oxide, silicon carbide, and molecular sieves.

[0018] 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.

[0019] In another preferred embodiment, the pretreatment in step (1) includes: immersion in a strong acid solution at 30-100 °C for 1-24 hours.

[0020] In another preferred embodiment, the pretreatment temperature is 50-80 °C.

[0021] In another preferred embodiment, the pretreatment time is 5-10 hours.

[0022] In another preferred embodiment, after the pretreatment is completed, the method further includes: washing with deionized water until the pH is neutral, and drying at 50-150 °C for later use.

[0023] In another preferred embodiment, the drying temperature is 80-120 °C.

[0024] In another preferred embodiment, 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.

[0025] In another preferred embodiment, 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.

[0026] 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 combinations thereof.

[0027] In another preferred embodiment, the nitrogen-containing precursor is selected from the group consisting of: ammonia, ammonium salts, nitric acid, C1-C10 amines, and C1-C10 nitro compounds.

[0028] 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, and lactams.

[0029] In another preferred embodiment, the sulfur-containing precursor is selected from the group consisting of sulfuric acid, sulfates, C1-C10 thiol compounds, and C1-C10 thiourea compounds.

[0030] In another preferred embodiment, the phosphorus-containing compound is selected from the group consisting of: phosphoric acid, phosphates, organophosphorus compounds, triphenylphosphine, and diethylphosphine.

[0031] In another preferred embodiment, the boron-containing precursor is selected from the group consisting of: boric acid, borax, and organoboron compounds;

[0032] In another preferred embodiment, in the modification process of step (2):

[0033] The mass ratio of oxygen atoms to the support in the oxygen-containing precursor is 1:0.1~10, preferably 1:0.1~0.3; and / or;

[0034] The mass ratio of nitrogen atoms to the support in the nitrogen-containing precursor is 1:0.1~10, preferably 1:0.3~0.8; and / or;

[0035] The mass ratio of sulfur atoms to the support in the sulfur-containing precursor is 1:0.1~10, preferably 1:0.8~3; and / or;

[0036] The mass ratio of phosphorus atoms to the support in the phosphorus-containing precursor is 1:0.1~10, preferably 1:3~5; and / or;

[0037] The mass ratio of boron atoms to the support in the boron-containing precursor is 1:0.1~10, preferably 1:5~10.

[0038] In another preferred embodiment, in step (2), the carrier modification is performed with the assistance of ultrasound, and the ultrasound frequency is 20~100KHZ.

[0039] In another preferred embodiment, the ultrasound duration is 0.1 to 10 hours.

[0040] In another preferred embodiment, step (2) of the method further includes drying the ultrasonically treated carrier at 50~150 °C.

[0041] In another preferred embodiment, in step (2), the method further includes: drying and then calcining at 500~1000℃ to obtain a surface-modified carrier.

[0042] In another preferred embodiment, the roasting time is 1-3 hours.

[0043] In another preferred embodiment, in step (3), the catalytically active metal salt is selected from the group consisting of MnCl3, TiCl3, PbCl4, CeCl3, IrCl3, PuCl5, CuCl2, CuCl, BiCl3, TiCl4, VCl4, or a combination thereof.

[0044] In another preferred embodiment, the catalytically active metal salt comprises at least two components selected from the group consisting of MnCl3, TiCl3, PbCl4, CeCl3, IrCl3, PuCl5, CuCl2, CuCl, BiCl3, TiCl4, VCl4, or combinations thereof.

[0045] In another preferred embodiment, the total mass ratio of the catalytically active metal salt component to the support is 1:0.1~50.

[0046] In another preferred embodiment, in step (3), 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.

[0047] In another preferred embodiment, the mass ratio of the co-catalytic metal salt to the support is 1:0.1~100.

[0048] In another preferred embodiment, in step (3), the coordination compound is selected from the group consisting of phosphorus-containing coordination compounds (such as H3PO4, triethyl phosphite, butyl phosphite, triphenylphosphite, or combinations thereof), sulfur-containing coordination compounds (such as thiourea, ammonium persulfate, sodium persulfate, potassium thiocyanate, or combinations thereof), nitrogen-containing coordination compounds (such as ammonium chloride, methylpyrrolidone, N,N-diethylacetamide, 1,10-o-phenegrin), or combinations thereof.

[0049] In another preferred embodiment, the mass ratio of the coordination compound to the support is 1:0.1~50.

[0050] In another preferred embodiment, in step (4), the impregnation includes vacuum impregnation, and preferably, the vacuum impregnation time is 0.1 to 10 hours.

[0051] In another preferred embodiment, in step (4), the impregnation includes ultrasonic-assisted impregnation, preferably, the ultrasonic frequency is 20~100KHZ.

[0052] In another preferred embodiment, in step (4), the ultrasound time is 0.1 to 10 hours.

[0053] In another preferred embodiment, step (5) further includes drying the sample after counter-rotation drying at 50~150 °C.

[0054] It should be understood that, within the scope of this invention, the above-described technical features of this invention and the technical features specifically described below (such as in the embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be described in detail here. Attached Figure Description

[0055] Figure 1 This is a flow chart of the catalyst preparation process of the present invention. Detailed Implementation

[0056] This invention addresses the shortcomings of existing technologies by providing a method for the hydrochlorination of acetylene. The non-mercury catalyst provided by this invention exhibits high catalytic activity and good stability, fully meeting the needs of industrial vinyl chloride production, and is also environmentally friendly with low production costs.

[0057] Non-precious metal composite catalysts for alkyne addition reactions

[0058] Previous patents and literature mainly focused on selecting ligands and auxiliaries based on elements such as copper, bismuth, tin, cadmium, titanium, and barium as the main active components, lacking innovation in the selection of active components, thus failing to significantly alter catalytic activity. Based on the catalytic mechanism of acetylene hydrochlorination, the more stable the intermediate complex C2H2-MClx formed by acetylene and metal salt, the higher the catalytic activity and the higher the selectivity of the product vinyl chloride. As an electron-donating molecule, acetylene has a high electron cloud density, making it easily adsorbed and activated by ions or molecules with high standard potentials. In other words, metal ions with high standard potentials exhibit higher catalytic activity in the acetylene hydrochlorination reaction. Based on this principle, this invention screened a large number of non-noble metal compounds with high standard potentials as active components for evaluation and verification. The evaluation results showed that metal compounds with high standard potentials exhibited high catalytic activity, leading to the acquisition of a highly active non-mercury catalyst.

[0059] The non-noble metal composite catalyst of the present invention is prepared by the following method:

[0060] (1) The catalyst support is pretreated under certain conditions to obtain the pretreated catalyst support;

[0061] (2) The catalyst support after step (1) is modified under certain conditions to regulate the surface groups of the support and improve the dispersion and fixation of the catalytic active components.

[0062] (3) Prepare the following solutions in sequence: catalytic active component metal salt solution; co-catalytic metal salt solution; alkali metal salt solution; rare earth metal salt solution; coordination compound solution;

[0063] (4) Mix and impregnate the modified catalyst support from step (2) with the solutions obtained in step (3);

[0064] (5) The impregnated sample is dried and calcined to obtain a non-mercury catalyst for catalyzing the hydrochlorination reaction of acetylene.

[0065] In the above method, the preferred step (1) further includes one or more of the following features:

[0066] The catalyst supports can be activated carbon, alumina, silica, silicon carbide, or molecular sieves.

[0067] The catalyst support can be pretreated using 2N hydrochloric acid solution, 2N nitric acid solution, or 2N sulfuric acid solution at 30-100℃ for 1-24 hours, washed with deionized water until pH neutral, and dried at 50-150℃ for later use. More preferably, the pretreatment temperature is 50-80℃, the pretreatment time is 5-10 hours, and the drying temperature is 80-120℃.

[0068] Preferably, step (2) above further includes one or more of the following features:

[0069] In step (2), the surface modification of the carrier includes modification with oxygen, nitrogen, sulfur, phosphorus, and boron atoms. Oxygen-containing precursors mainly include compounds such as alcohols, aldehydes, acids, and esters, including but not limited to nitric acid, ethylene glycol, furfural, acetic acid, citric acid, and ethyl acetate. Nitrogen-containing precursors mainly include compounds such as amino, nitro, and amino groups, including but not limited to ammonia, ammonium chloride, nitric acid, acrylamide, uric acid, imidazole, pyridine, pyrrole, and lactams. Sulfur-containing precursors mainly include but not limited to sulfuric acid and sulfates, mercapto compounds, and thiourea. Phosphorus-containing compounds include but are not limited to phosphoric acid, phosphates, organophosphorus compounds, triphenylphosphine, and diethylphosphine. Boron-containing precursors include but are not limited to boric acid, borax, and organoboron compounds.

[0070] The modifier precursor compound in step (2) can be used for carrier modification in one or more ways. The amount of modifier is based on the mass ratio of oxygen, nitrogen, sulfur, phosphorus or boron atoms to the carrier of 1:0.1~10, such as 1:0.1~0.3, 1:0.3~0.8, 1:0.8~3, 1:3~5, 1:5~10.

[0071] In step (2), the carrier modification is preferably carried out under ultrasonic assistance, with an ultrasonic frequency of 20~100KHZ, such as 20~40KHZ, 40-60KHZ, 60~80KHZ, or 80~100KHZ. The ultrasonic time is 0.1~10 hours, such as 0.1~2 hours, 2~4 hours, 4~6 hours, 6~8 hours, or 8~10 hours.

[0072] Preferably, step (2) further includes: drying the ultrasonically treated carrier at 50~150 ℃, such as 50~70 ℃, 70~100 ℃, 100~120 ℃, 120~150 ℃; and calcining it at 500~1000 ℃ for 2 hours after drying, such as 500~600 ℃, 600~700 ℃, 700~800 ℃, 800~900 ℃, 900~1000 ℃.

[0073] In another preferred embodiment, step (3) further includes one or more of the following:

[0074] In step (3), the non-precious metal catalytic active components mainly include metal salts with high standard potential, including but not limited to one or more of MnCl3, TiCl3, PbCl4, CeCl3, IrCl3, PuCl5, CuCl2, CuCl, BiCl3, TiCl4, and VCl4; the total mass ratio of the active components to the support mass 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), and 1: (40~50).

[0075] 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).

[0076] 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).

[0077] In another preferred embodiment, step (4) includes one or more of the following features:

[0078] 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.

[0079] After vacuum impregnation in step (4), ultrasonic-assisted impregnation is performed. The ultrasonic frequency is 20~100KHZ, for example, 20~40KHZ, 40-60KHZ, 60~80KHZ, or 80~100KHZ. The ultrasonic time is 0.1~10 hours, for example, 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.

[0080] In another preferred embodiment, step (5) includes one or more of the following features:

[0081] In step (5), the sample that has been evaporated by rotary drying is dried at 50~150 ℃, such as 50~70 ℃, 70~100 ℃, 100~120 ℃, 120~150 ℃; after drying, it is calcined at 500~1000 ℃ for 2 hours, such as 500~600 ℃, 600~700 ℃, 700~800 ℃, 800~900 ℃, 900~1000 ℃.

[0082] Acetylene hydrochlorination reaction using a non-precious metal composite catalyst

[0083] The non-precious metal composite catalyst prepared by this invention can achieve good catalytic activity and high conversion rate when used in the acetylene hydrochlorination reaction.

[0084] When used in the hydrogen chloride addition reaction of acetylene, the catalyst is loaded into a fixed-bed reaction tube, and hydrogen chloride and acetylene are introduced to react. Preferably, the method further includes one or more of the following features:

[0085] The molar ratio of acetylene to hydrogen chloride feedstock 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).

[0086] In the acetylene hydrochlorination reaction, the volume hourly space velocity (based on acetylene) is 10–150 h⁻¹. -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 .

[0087] The pressure for acetylene hydrochlorination reaction 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, and 0.9~1.0 MPa.

[0088] The preferred temperature for the acetylene hydrochlorination reaction is 80~180 ℃, such as 80~100 ℃, 100~120 ℃, 120~140 ℃, 140~160 ℃, or 160~180 ℃.

[0089] The reaction product obtained after hydrochlorination can be cooled, compressed, frozen, separated, and then distilled to obtain vinyl chloride monomer.

[0090] This invention abandons the blind approach in traditional catalyst preparation processes, focusing instead on the catalytic mechanism of acetylene hydrochlorination. It scientifically screens and discovers catalytically active components and the chemical interactions between different compounds to achieve a synergistic catalytic effect. Based on this approach, we have developed a highly active catalyst that significantly improves activity compared to previously reported non-precious metal catalysts. Having identified the catalytic components, we further screen different promoters and coordination compounds based on catalytic theory to enhance catalyst stability.

[0091] The significance of this invention lies in the development of a novel non-mercury catalyst that can completely replace the existing mercury-catalyst for the industrial production of vinyl chloride, without causing environmental damage, and is thus an environmentally friendly catalyst.

[0092] The main technical effects of this invention are as follows:

[0093] 1) This invention starts from the mechanism of acetylene hydrochlorination reaction and screens a large number of non-noble metal salts with high standard electrode potentials. The synergistic effect of these metal ions exhibits characteristics similar to noble metal salts, strongly adsorbing and activating acetylene molecules, resulting in very high catalytic activity and catalytic stability at 120℃ and acetylene space velocity of 30h⁻¹. -1 Under normal pressure, the initial single-pass conversion rate of acetylene can reach 95%, and the selectivity of vinyl chloride is greater than 98%.

[0094] 2) Since the standard electrode potentials of alkali metal and rare earth metal ions are negative, they can demonstrate the stabilizing effect of the catalyst; the addition of some coordination compound molecules improves the dispersion and fixation of the active components, reducing losses during the reaction; in addition, the use of vacuum and ultrasonic-assisted impregnation improves the dispersion and fixation of the active components, thereby improving the catalyst stability. The non-mercury catalyst prepared in this invention achieved a stability of 500 hours in a single-tube small-scale test.

[0095] This invention uses non-precious metals as raw materials, which is much cheaper than precious metal catalysts and is environmentally friendly. The catalyst's operating conditions are very similar to those of existing mercury catalysts, so it can be used in existing acetylene process industrial production with just a simple replacement.

[0096] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. Percentages and parts are by weight unless otherwise stated.

[0097] Preparation Example

[0098] Examples 1-9 below relate to the preparation of non-noble metal composite catalysts. Unless otherwise specified, the main implementation steps include:

[0099] (1) The catalyst support is pretreated under certain conditions to obtain the pretreated catalyst support;

[0100] (2) The catalyst support after step (1) is modified under certain conditions to regulate the surface groups of the support and improve the dispersion and fixation of the catalytic active components;

[0101] (3) Prepare the following solutions in sequence: catalytic active component metal salt solution; co-catalytic metal salt solution; alkali metal salt solution; rare earth metal salt solution; coordination compound solution;

[0102] (4) Mix and impregnate the modified catalyst support from step (2) with the solutions obtained in step (3);

[0103] (5) The impregnated sample is dried and calcined to obtain a non-mercury catalyst for catalyzing the hydrochlorination reaction of acetylene.

[0104] Example 1

[0105] (1) Weigh 10g of 40-mesh activated carbon, pretreat it with 2N hydrochloric acid solution at 60℃ for 4 hours, then wash it with deionized water until pH is neutral, and then dry it at 100℃ for 10 hours for later use.

[0106] (2) The pretreated activated carbon was mixed with 2N nitric acid and ammonium chloride solution, and the mass ratio of nitrogen atoms to activated carbon was controlled at 1:10. The mixture was ultrasonically impregnated at 50KHZ for 2 hours. After ultrasonic impregnation, the carbon was dried at 110 ℃ for 12 hours and then placed in a tube furnace and calcined under nitrogen atmosphere for 2 hours to obtain the modified activated carbon.

[0107] (3) Weigh a mixture of MnCl3 and PbCl4, control the mass ratio of MnCl3 and PbCl4 to activated carbon at 1:10, and dissolve it in water to obtain solution I; weigh an appropriate amount of LiCl and LaCl3, control the mass ratio of LiCl and PbCl3 to activated carbon at 1:20, and dissolve them in water to obtain solution II; weigh an appropriate amount of triethyl phosphite, control the mass ratio of triethyl phosphite to activated carbon at 1:15, and dissolve it in water and ethanol to obtain solution III.

[0108] (4) After mixing the three solutions I, II and III, the modified activated carbon is added for impregnation. First, it is impregnated under vacuum for 2 hours, and then impregnated for 3 hours under ultrasonic assistance at 50 KHZ. Then, the water is removed by rotary evaporation to obtain a preliminarily dried sample.

[0109] (5) The pre-dried sample was dried at 120 °C for 5 hours, and then placed in a tube furnace at 500 °C under a nitrogen atmosphere for 2 hours to obtain the non-mercury catalyst C1.

[0110] Example 2

[0111] (1) Weigh 10g of 40-mesh activated carbon, pretreat it with 2N nitric acid solution at 80℃ for 3 hours, then wash it with deionized water until pH is neutral, and then dry it at 120℃ for 5 hours for later use.

[0112] (2) The pretreated activated carbon was mixed with acrylamide and ammonium sulfate solution, and the mass ratio of nitrogen and sulfur atoms to activated carbon was controlled at 1:5. It was ultrasonically impregnated at 70KHZ for 4 hours. After ultrasonic impregnation, it was dried at 130 ℃ for 8 hours and then placed in a tube furnace and calcined under nitrogen atmosphere for 2 hours to obtain the modified activated carbon.

[0113] (3) Weigh a mixture of TiCl3 and IrCl3, control the mass ratio of TiCl3 and IrCl3 to activated carbon at 1:20, and dissolve it in water to obtain solution I; weigh an appropriate amount of BaCl2 and LaCl3, control the mass ratio of TiCl2 and IrCl3 to activated carbon at 1:30, and dissolve them in water to obtain solution II; weigh an appropriate amount of triphenylphosphine, control the mass ratio of triphenylphosphine to activated carbon at 1:20, and dissolve it in water and ethanol to obtain solution III.

[0114] (4) After mixing the three solutions I, II and III, the modified activated carbon is added for impregnation. First, it is impregnated under vacuum for 4 hours, and then impregnated for 6 hours under ultrasonic assistance at 50 KHZ. Then, the water is removed by rotary evaporation to obtain a preliminarily dried sample.

[0115] (5) The pre-dried sample was dried at 100 °C for 10 hours, and then placed in a tube furnace at 500 °C under a nitrogen atmosphere for 2 hours to obtain a non-mercury catalyst C2;

[0116] Example 3

[0117] (1) Weigh 10g of 40-mesh activated carbon, pretreat it with 2N nitric acid solution at 60℃ for 6 hours, then wash it with deionized water until pH is neutral, and then dry it at 150℃ for 4 hours for later use.

[0118] (2) The pretreated activated carbon was mixed with urea and thiourea solution, and the mass ratio of nitrogen and sulfur atoms to activated carbon was controlled at 1:10. The mixture was ultrasonically impregnated at 60 KHZ for 4 hours. After ultrasonic impregnation, the carbon was dried at 100 °C for 12 hours and then placed in a tube furnace and calcined under nitrogen atmosphere for 2 hours to obtain the modified activated carbon.

[0119] (3) Weigh a mixture of CeCl3 and BiCl3, control the mass ratio of CeCl3 and BiCl3 to activated carbon at 1:10, and dissolve it in water to obtain solution I; weigh an appropriate amount of SrCl2 and EuCl3, control the mass ratio of SrCl2 and EuCl3 to activated carbon at 1:40, and dissolve them in water to obtain solution II; weigh an appropriate amount of potassium thiocyanate, control the mass ratio of potassium thiocyanate to activated carbon at 1:20, and dissolve it in water and ethanol to obtain solution III;

[0120] (4) After mixing the three solutions I, II and III, the modified activated carbon is added for impregnation. First, it is impregnated under vacuum for 3 hours, and then impregnated for 8 hours under ultrasonic assistance at 60 KHZ. Then, the water is removed by rotary evaporation to obtain a preliminarily dried sample.

[0121] (5) The preliminarily dried sample was dried at 120 °C for 8 hours, and then placed in a tube furnace at 550 °C under a nitrogen atmosphere for 2 hours to obtain the non-mercury catalyst C3.

[0122] Example 4

[0123] (1) Weigh 10g of 50-mesh activated carbon, pretreat it with 2N hydrochloric acid solution at 80℃ for 5 hours, then wash it with deionized water until pH is neutral, and then dry it at 120℃ for 8 hours for later use.

[0124] (2) The pretreated activated carbon was mixed with phosphoric acid and sulfuric acid solution, and the ratio of phosphorus and sulfur atomic mass to activated carbon mass was controlled at 1:8. The mixture was ultrasonically impregnated at 60KHZ for 5 hours. After ultrasonic impregnation, the carbon was dried at 120 ℃ for 6 hours and then placed in a tube furnace and calcined under nitrogen atmosphere for 2 hours to obtain the modified activated carbon.

[0125] (3) Weigh a mixture of PuCl5 and CuCl2, control the mass ratio of the mixture to activated carbon at 1:15, and dissolve it in water to obtain solution I; weigh an appropriate amount of CaCl2 and PrCl3, control the mass ratio of the mixture to activated carbon at 1:30, and dissolve it in water to obtain solution II; weigh an appropriate amount of methylpyrrolidone, control the mass ratio of the mixture to activated carbon at 1:20, and dissolve it in water and ethanol to obtain solution III;

[0126] (4) After mixing the three solutions I, II and III, the modified activated carbon is added for impregnation. First, it is impregnated under vacuum for 2 hours, and then impregnated for 6 hours under ultrasonic assistance at 60 KHZ. Then, the water is removed by rotary evaporation to obtain a preliminarily dried sample.

[0127] (5) The preliminarily dried sample was dried at 120 °C for 10 hours, and then placed in a tube furnace at 500 °C under a nitrogen atmosphere for 2 hours to obtain a non-mercury catalyst C4.

[0128] Example 5

[0129] (1) Weigh 10g of 50-mesh activated carbon, pretreat it with 2N hydrochloric acid solution at 60℃ for 10 hours, then wash it with deionized water until pH is neutral, and then dry it at 130℃ for 5 hours for later use.

[0130] (2) The pretreated activated carbon was mixed with ammonium hydrogen phosphate and borax solution, and the atomic mass ratio of phosphorus and boron to activated carbon was controlled at 1:10. The mixture was ultrasonically impregnated at 60KHZ for 4 hours. After ultrasonic impregnation, the carbon was dried at 150 ℃ for 4 hours and then placed in a tube furnace and calcined under nitrogen atmosphere for 2 hours to obtain the modified activated carbon.

[0131] (3) Weigh a mixture of CuCl2 and BiCl3, control the mass ratio of CuCl2 and BiCl3 to activated carbon at 1:5, and dissolve it in water to obtain solution I; weigh an appropriate amount of KCl and PrCl3, control the mass ratio of KCl and PrCl3 to activated carbon at 1:20, and dissolve them in water to obtain solution II; weigh an appropriate amount of N-methyllactam, control the mass ratio of N-methyllactam to activated carbon at 1:50, and dissolve it in water and ethanol to obtain solution III;

[0132] (4) After mixing the three solutions I, II and III, the modified activated carbon is added for impregnation. First, it is impregnated under vacuum for 4 hours, and then impregnated under 70 KHZ ultrasonic assistance for 2 hours. Then, the water is removed by rotary evaporation to obtain a preliminarily dried sample.

[0133] (5) The pre-dried sample was dried at 150 °C for 5 hours and then placed in a tube furnace at 550 °C under a nitrogen atmosphere for 2 hours to obtain the non-mercury catalyst C5.

[0134] Example 6

[0135] (1) Weigh 10g of 50-mesh activated carbon, pretreat it with 2N hydrochloric acid solution at 70 °C for 8 hours, then wash it with deionized water until pH is neutral, and then dry it at 110 °C for 6 hours for later use.

[0136] (2) The pretreated activated carbon was mixed with ammonium hydrogen phosphate and borax solution, and the atomic mass ratio of phosphorus and boron to activated carbon was controlled at 1:15. The mixture was ultrasonically impregnated at 60 KHZ for 5 hours. After ultrasonic impregnation, the carbon was dried at 120 °C for 6 hours and then placed in a tube furnace and calcined under nitrogen atmosphere for 2 hours to obtain the modified activated carbon.

[0137] (3) Weigh a mixture of BiCl3 and TiCl4, control the mass ratio of BiCl3 and TiCl4 to activated carbon at 1:8, and dissolve it in water to obtain solution I; weigh an appropriate amount of CsCl and PrCl3, control the mass ratio of CsCl and PrCl3 to activated carbon at 1:15, and dissolve it in water to obtain solution II; weigh an appropriate amount of N,N-diethylacetamide, control the mass ratio of N,N-diethylacetamide to activated carbon at 1:30, and dissolve it in water and ethanol to obtain solution III;

[0138] (4) After mixing the three solutions I, II and III, the modified activated carbon is added for impregnation. First, it is impregnated under vacuum for 6 hours, and then impregnated for 2 hours under ultrasonic assistance at 60 KHZ. Then, the water is removed by rotary evaporation to obtain a preliminarily dried sample.

[0139] (5) The pre-dried sample was dried at 120°C for 6 hours and then placed in a tube furnace at 600°C under a nitrogen atmosphere for 2 hours to obtain the non-mercury catalyst C6.

[0140] Example 7

[0141] (1) Weigh 10g of 40-mesh activated carbon, pretreat it with 2N hydrochloric acid solution at 50°C for 10 hours, then wash it with deionized water until pH is neutral, and then dry it at 140°C for 8 hours for later use.

[0142] (2) The pretreated activated carbon was mixed with pyridine and borax solution, and the mass ratio of nitrogen and boron atomic mass to activated carbon was controlled at 1:10. It was ultrasonically impregnated at 60 KHZ for 8 hours. After ultrasonic impregnation, it was dried at 80 °C for 20 hours and then placed in a tube furnace and calcined under nitrogen atmosphere for 2 hours to obtain the modified activated carbon.

[0143] (3) Weigh a mixture of CuCl2 and TiCl4, control the mass ratio of CuCl2 and TiCl4 to activated carbon at 1:10, and dissolve it in water to obtain solution I; weigh an appropriate amount of LiCl and LaCl3, control the mass ratio of LiCl and LaCl3 to activated carbon at 1:20, and dissolve them in water to obtain solution II; weigh an appropriate amount of 1,10-o-Frenchlin, control the mass ratio of Frenchlin to activated carbon at 1:20, and dissolve it in water and ethanol to obtain solution III;

[0144] (4) After mixing the three solutions I, II and III, the modified activated carbon is added for impregnation. First, it is impregnated under vacuum for 3 hours, and then impregnated for 2 hours under the assistance of 70 KHZ ultrasound. Then, the water is removed by rotary evaporation to obtain a preliminarily dried sample.

[0145] (5) The preliminarily dried sample was dried at 150°C for 6 hours, and then placed in a tube furnace at 500°C under a nitrogen atmosphere for 2 hours to obtain the non-mercury catalyst C7.

[0146] Example 8

[0147] (1) Weigh 10g of 40-mesh activated carbon, pretreat it with 2N hydrochloric acid solution at 60°C for 8 hours, then wash it with deionized water until the pH is neutral, and then dry it at 120°C for 6 hours for later use.

[0148] (2) The pretreated activated carbon was mixed with pyridine and borax solution, and the mass ratio of nitrogen and boron atomic mass to activated carbon was controlled at 1:15. It was ultrasonically impregnated at 60 KHZ for 6 hours. After ultrasonic impregnation, it was dried at 60 °C for 20 hours and then placed in a tube furnace and calcined under nitrogen atmosphere for 2 hours to obtain the modified activated carbon.

[0149] (3) Weigh a mixture of CuCl2, CeCl3 and TiCl4, control the mass ratio of CuCl2 and CeCl3 to activated carbon at 1:12, and dissolve it in water to obtain solution I; weigh an appropriate amount of BaCl2 and LaCl3, control the mass ratio of BaCl2 and CeCl3 to activated carbon at 1:25, and dissolve them in water to obtain solution II; weigh an appropriate amount of ammonium persulfate, control the mass ratio of Ammonium persulfate to activated carbon at 1:15, and dissolve it in water and ethanol to obtain solution III;

[0150] (4) After mixing the three solutions I, II and III, the modified activated carbon is added for impregnation. First, it is impregnated under vacuum for 5 hours, and then impregnated for 4 hours under the assistance of 70 KHZ ultrasound. Then, the water is removed by rotary evaporation to obtain a preliminarily dried sample.

[0151] (5) The preliminarily dried sample was dried at 120°C for 4 hours, and then placed in a tube furnace at 500°C under a nitrogen atmosphere for 2 hours to obtain the non-mercury catalyst C8.

[0152] Example 9

[0153] (1) Weigh 10g of 40-mesh activated carbon, pretreat it with 2N hydrochloric acid solution at 80℃ for 6 hours, then wash it with deionized water until pH is neutral, and then dry it at 140℃ for 4 hours for later use.

[0154] (2) The pretreated activated carbon was mixed with pyridine and borax solution, and the mass ratio of nitrogen and boron atomic mass to activated carbon was controlled at 1:20. It was ultrasonically impregnated at 60 KHZ for 6 hours. After ultrasonic impregnation, it was dried at 80 ℃ for 16 hours and then placed in a tube furnace and calcined under nitrogen atmosphere for 2 hours to obtain the modified activated carbon.

[0155] (3) Weigh a mixture of CuCl2, CeCl3, TiCl4 and VCl4, control the mass ratio of CuCl2 to activated carbon at 1:10, and dissolve it in water to obtain solution I; weigh an appropriate amount of KCl and LaCl3, control the mass ratio of KCl to activated carbon at 1:15, and dissolve it in water to obtain solution II; weigh an appropriate amount of thiourea, control the mass ratio of thiourea to activated carbon at 1:20, and dissolve it in water and ethanol to obtain solution III;

[0156] (4) After mixing the three solutions I, II and III, the modified activated carbon is added for impregnation. First, it is impregnated under vacuum for 6 hours, and then impregnated under ultrasonic assistance at 70 KHZ for 6 hours. Then, the water is removed by rotary evaporation to obtain a preliminarily dried sample.

[0157] (5) The preliminarily dried sample was dried at 150°C for 4 hours, and then placed in a tube furnace at 550°C under a nitrogen atmosphere for 2 hours to obtain the non-mercury catalyst C9.

[0158] Comparative Example 1

[0159] (1) Weigh 10g of 40-mesh activated carbon, pretreat it with 2N hydrochloric acid solution at 60℃ for 6 hours, then wash it with deionized water until pH is neutral, and then dry it at 120℃ for 5 hours for later use.

[0160] (2) The pretreated activated carbon was mixed with pyridine and borax solution, and the mass ratio of nitrogen and boron atomic mass to activated carbon was controlled at 1:15. It was ultrasonically impregnated at 60 KHZ for 8 hours. After ultrasonic impregnation, it was dried at 60 °C for 16 hours and then placed in a tube furnace and calcined under nitrogen atmosphere for 2 hours to obtain the modified activated carbon.

[0161] (3) Weigh CuCl2, control the mass ratio of CuCl2 to activated carbon at 1:10, and dissolve it in water to obtain solution I; weigh an appropriate amount of KCl and LaCl3, control their mass ratio with activated carbon at 1:20, and dissolve them in water to obtain solution II; weigh an appropriate amount of thiourea, control its mass ratio with activated carbon at 1:20, and dissolve it in water and ethanol to obtain solution III.

[0162] (4) After mixing the three solutions I, II and III, the modified activated carbon is added for impregnation. First, it is impregnated under vacuum for 5 hours, and then impregnated for 4 hours under the assistance of 70 KHZ ultrasound. Then, the water is removed by rotary evaporation to obtain a preliminarily dried sample.

[0163] (5) The preliminarily dried sample was dried at 120°C for 6 hours, and then placed in a tube furnace at 500°C under a nitrogen atmosphere for 2 hours to obtain a non-mercury catalyst C10.

[0164] Test Implementation Examples

[0165] In this section, the C1-C10 non-precious metal composite catalyst prepared in the first part is used for evaluation in the reaction.

[0166] Test Example 1: Catalytic hydrochlorination of acetylene:

[0167] Take 1g of C1-C10 catalyst sample and pack it into a 10mm diameter reaction tube. Evaluate the catalyst activity and stability using a fixed-bed reactor with an acetylene to hydrogen chloride molar ratio of 1:(1~1.5) and an acetylene space velocity of 10~150h⁻¹. -1 The reaction temperature was 80~180℃, and the reaction pressure was 0~1MPa. The gaseous products were analyzed by gas chromatography. The catalyst evaluation results are shown in Table 1 (the acetylene conversion rate in the table is the initial maximum conversion rate).

[0168] Table 1 Evaluation results of C1-C10 catalysts

[0169]

[0170] As can be seen from the results in the table above, the catalyst of this invention exhibits good catalytic activity and selectivity in the catalytic hydrochlorination of acetylene. In particular, the catalytic activity is significantly enhanced when two or three catalytically active metal salts are used in synergistic effects.

[0171] All documents mentioned in this invention are incorporated herein by reference as if each document were individually incorporated by reference. Furthermore, it should be understood that after reading the foregoing teachings of this invention, those skilled in the art can make various alterations or modifications to this invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. A process for the production of chloroethene from acetylene and hydrogen chloride, characterized in that, The method comprises the following steps: The catalyst is loaded into a fixed bed reaction tube, and the acetylene and the hydrogen chloride pass through the reaction tube to react; wherein the catalyst is prepared by the following method: (1) pretreating the catalyst carrier with a strong acid solution to obtain a pretreated catalyst carrier; (2) modifying the catalyst carrier treated in step (1) to obtain a catalyst carrier with surface groups; (3) providing a catalytically active component metal salt solution, a cocatalytic metal salt solution, and a coordination compound solution; (4) mixing the catalyst carrier with surface groups in step (2) with the solutions obtained in step (3) for impregnation to obtain an impregnated sample; (5) drying and calcining the impregnated sample obtained in step (4) to obtain a non-noble metal composite catalyst for catalyzing acetylene addition reaction; The catalytically active component metal salt comprises at least two components selected from the group consisting of CeCl3, CuCl2, BiCl3, and TiCl4. The cocatalytic metal salt comprises at least two components selected from the group consisting of KCl, BaCl2, SrCl2, LaCl3, and EuCl3. The coordination compound is selected from the group consisting of thiourea, ammonium persulfate, sodium persulfate, and potassium thiocyanate.

2. The method of claim 1, wherein, In the method, the molar ratio of acetylene to hydrogen chloride raw material is 1:1-1.

5.

3. The method of claim 1, wherein, In the method, the volume space velocity of the acetylene hydrochlorination reaction is 10-150 h -1 , based on acetylene.

4. The method of claim 1, wherein, In the method, the acetylene hydrochlorination reaction pressure is 0-1 MPa.

5. The method of claim 1, wherein, In the method, the reaction temperature is 80-180℃.

6. The method of claim 1, wherein, The catalyst carrier is selected from the group consisting of activated carbon, alumina, silicon oxide, silicon carbide, and molecular sieve.

7. The method of claim 1, wherein, In step (1), the strong acid is selected from the group consisting of hydrochloric acid, nitric acid, and sulfuric acid.

8. The method of claim 1, wherein, In step (1), the pretreatment comprises impregnation treatment with a strong acid solution at 30-100℃ for 1-24 hours.

9. The method of claim 1, wherein, In step (2), the modification treatment comprises modifying the carrier with a precursor selected from the group consisting of oxygen-containing precursor, nitrogen-containing precursor, sulfur-containing precursor, phosphorus-containing precursor, and boron-containing precursor.

10. The method of claim 9, wherein, The oxygen-containing precursor is selected from the group consisting of C1-C10 alcohol reagent, C1-C10 aldehyde reagent, C1-C10 acid reagent, and C1-C10 ester reagent.

11. The method of claim 9, wherein, The nitrogen-containing precursor is selected from the group consisting of ammonia, ammonium salt, nitric acid, C1-C10 amine, and C1-C10 nitro compound.

12. The method of claim 9, wherein, The sulfur-containing precursor is selected from the group consisting of sulfuric acid, sulfate, C1-C10 mercapto compound, and C1-C10 thiourea compound.

13. The method of claim 9, wherein, The phosphorus-containing compound is selected from the group consisting of phosphoric acid, phosphate, and organic phosphorus compound.

14. The method of claim 13, wherein, The phosphorus-containing compound is selected from the group consisting of triphenylphosphine and diethylphosphine.

15. The method of claim 9, wherein, The boron-containing precursor is selected from the group consisting of boric acid, borax, and organic boron compound.

16. The method of claim 9, wherein, In the modification treatment of step (2): The mass ratio of oxygen atoms in the oxygen-containing precursor to the carrier is 1:0.1-10; and / or; The mass ratio of nitrogen atoms in the nitrogen-containing precursor to the carrier is 1:0.1-10; and / or; The mass ratio of the sulfur atom in the sulfur-containing precursor to the carrier is 1:0.1-10; and / or; The mass ratio of the phosphorus atom in the phosphorus-containing precursor to the carrier is 1:0.1-10; and / or; The mass ratio of the boron atom in the boron-containing precursor to the carrier is 1:0.1-10.

17. The method of claim 1, wherein, In the step (3), the metal salt of the catalytically active component is: CeCl3 and BiCl3; or CeCl3, CuCl2 and TiCl4.

18. The method of claim 1, wherein, The total mass ratio of the metal salt of the catalytically active component to the carrier is 1:0.1-50.

19. The method of claim 1, wherein, In the step (3), the metal salt of the catalytically active component is: SrCl2 and EuCl3; or BaCl2 and LaCl3; or KCl and LaCl3.

20. The method of claim 1, wherein, The mass ratio of the metal salt of the catalytically active component to the carrier is 1:0.1-50.

21. The method of claim 1, wherein, In the step (3), the metal salt of the catalytically active component is:

22. The method of claim 1, wherein, SrCl2 and EuCl3; or BaCl2 and LaCl3; or KCl and LaCl3. The mass ratio of the metal salt of the catalytically active component to the carrier is 1:0.1-50. In the step (3), the complexing compound is selected from the group consisting of thiourea, ammonium persulfate, potassium thiocyanate, or a combination thereof. The mass ratio of the complexing compound to the carrier is 1:0.1-50.

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