Method for applying high-stability copper-based catalyst to acetylene hydrochlorination reaction

Abstract

The invention relates to a preparation method of a high-stability copper-based catalyst for acetylene hydrochlorination reaction, which comprises the following steps: by taking P3 (diethyl p-toluenesulfonyloxymethylphosphonate) as a phosphorus modifier, commercial activated carbon as a carrier, copper chloride as a main active component and absolute ethyl alcohol as a solvent, preparing a copper-based catalyst by a hydrothermal method; the phosphorus-modified high-stability copper-based catalyst is prepared by improving the synthesis steps, and the inactivation condition of the catalyst in the reaction process is inhibited while the performance of the copper-based catalyst is improved. The catalyst has relatively high activity and vinyl chloride selectivity in a reaction for preparing vinyl chloride through acetylene hydrochlorination on a fixed bed, is relatively low in cost and has relatively high industrial application value. Under the conditions that the reaction gas space velocity is 170h <-1 >, V (C2H2) / V (HCl) is 1: 1.05 and the reaction temperature is 180 DEG C, the acetylene conversion rate can reach 71%, the vinyl chloride selectivity is greater than 99%, and the activity is basically kept unchanged within 7.5 h.

Description

Technical Field

[0001] The invention belongs to the field of catalyst preparation technology and application, and specifically relates to a high-stability copper-based catalyst for acetylene hydrochlorination reaction and a preparation and application thereof. Background Art

[0002] As the world's second largest general-purpose resin, polyvinyl chloride has excellent chemical corrosion resistance and can resist corrosion from a variety of chemical substances such as acids, alkalis, and salts. It also has good electrical insulation properties, so it is widely used in construction, medicine, and industry. Limited by the characteristics of my country's energy structure, my country's current industrial production of vinyl chloride mainly uses the acetylene hydrochlorination method, which first reacts calcium carbide with water to produce acetylene, and then acetylene and hydrogen chloride react under the action of mercuric chloride catalyst to produce vinyl chloride. The advantage of this method is that the process is simple, but its energy consumption is high, and the mercuric chloride catalyst used is toxic and pollutes the environment to a certain extent. At present, about 70% of polyvinyl chloride resins in my country are synthesized by this method. The large-scale use of mercuric chloride catalysts has seriously harmed the environment and human health, so the research and development of mercury-free catalysts is imminent.

[0003] Copper is a relatively abundant and low-priced metal. Compared with precious metal catalysts, copper-based catalysts have significant cost advantages, can greatly reduce production costs, and have better economy. At the same time, through reasonable preparation methods and the addition of appropriate heteroatom ligands, additives, etc., the activity of copper-based catalysts can be significantly improved, so that they show good catalytic performance in acetylene hydrochlorination reaction. However, there is still a gap between its activity and that of precious metal catalysts: although the activity of copper-based catalysts can be improved through various improvement measures, its catalytic activity is still relatively low compared with precious metal catalysts such as Au and Ru. Under the same reaction conditions, it may not be able to achieve the same high conversion rate and selectivity as precious metal catalysts, which to a certain extent limits its application in some industrial productions that require extremely high reaction efficiency. At the same time, copper-based catalysts may still have problems such as loss of active components, agglomeration, and carbon deposition during long-term reactions, leading to catalyst deactivation. It is necessary to further optimize the preparation method and reaction conditions to improve its stability and service life.

[0004] Patent CN107008465A prepared a copper-based catalyst for acetylene hydrochlorination reaction with high activity and stability. The patent used coconut shell carbon as a carrier, copper chloride dihydrate and trimethylbenzyl ammonium chloride to prepare the catalyst, so that the mass fraction of copper in the catalyst is 5%, and the mass fraction of trimethylbenzyl ammonium chloride is 2.5%. At a reaction temperature of 180°C, a reaction pressure of normal pressure, and a volume space velocity of acetylene of 180h -1The reaction was carried out under the reaction conditions that the volume flow ratio of acetylene and hydrogen chloride gas was 1:1.1. The catalyst conversion rate decreased by 2.65% from the initial conversion rate of 48.08% in 12 hours. It can be seen that although the catalyst stability is improved, it still deactivates during the reaction process.

[0005] Although the above studies have modified the copper-based catalyst by introducing heteroatom ligands to improve the stability of the copper-based catalyst, it still suffers from deactivation during the reaction. Therefore, how to enhance the stability of the copper-based catalyst during the acetylene hydrochlorination reaction is of utmost importance for its industrial application. Summary of the invention

[0006] The technical problem solved by the present invention is to propose a method for using a high-stability copper-based catalyst for acetylene hydrochlorination reaction. The innovation of the method is that an organic phosphorus ligand is coordinated with copper ions to form a copper-ligand mixture, which is further anchored on the surface of activated carbon by roasting, thereby enhancing the stability of the copper-based catalyst. In this way, a copper-based catalyst with high stability and activity is prepared, the copper loading is 9%, the doping amount of phosphorus modifier is 1%, and the reaction gas space velocity is 170h -1 , V (C2H2) / V (HCl) =1:1.05, and the reaction temperature is 180℃, the acetylene conversion rate can reach 71%, the vinyl chloride selectivity is greater than 99%, and the activity remains basically unchanged after 7.5 h, providing a unique and effective solution for the low-cost and high-efficiency production of vinyl chloride in industry.

[0007] In order to solve the technical problem of the present invention, the technical solution proposed is: using the catalyst for the fixed-bed acetylene hydrochlorination reaction to produce vinyl chloride, at an acetylene space velocity of 170 h -1 , V (C2H2) / V (HCl) =1:1.05, vinyl chloride is produced under the condition of reaction temperature of 180℃;

[0008] The preparation method of the high stability copper-based catalyst for acetylene hydrochlorination reaction comprises the following steps:

[0009] (1) Weigh 0.476 g of diethyl p-toluenesulfonyloxymethylphosphonate and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir the mixture at 350 rpm with a magnetic stirrer at room temperature for 30 min to obtain an ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate.

[0010] (2) Weigh 1.107 g of cupric chloride dihydrate, pour it into the above-mentioned ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate, stir at room temperature for 5 h with a magnetic stirrer at 350 rpm to obtain a mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate;

[0011] (3) Using an electronic balance, 3 g of activated carbon was weighed and poured into the mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate, and stirred at room temperature for 24 h with a magnetic stirrer at 350 rpm. The mass ratio of copper in the catalyst: phosphorus in the modifier: carrier was 9:1:90.

[0012] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0013] (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 900°C at a heating rate of 5°C / min, and calcined for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0014] Preferably, in step (1), anhydrous ethanol is used as a solvent, and an appropriate amount of diethyl p-toluenesulfonyloxymethylphosphonate solid is dissolved in anhydrous ethanol at room temperature, and a magnetic stirrer is used to stir at 350 rpm for 30 min at room temperature.

[0015] Preferably, the mass ratio of the copper in step (2) to the phosphorus in diethyl p-toluenesulfonyloxymethylphosphonate is 9:1.

[0016] Preferably, the activated carbon in step (3) is in the shape of a column, powder or flake, with a particle size of 200 mesh and a specific surface area of ​​1000-1200m 2 / g.

[0017] Preferably, in step (3), the mass ratio of copper:phosphorus in the modifier:carrier is 9:1:90.

[0018] Preferably, the activated carbon in step (3) is in the shape of a column, powder or flake, with a particle size of 200 mesh and a specific surface area of ​​1000-1200m 2 / g.

[0019] Preferably, the catalyst after stirring in step (4) should be placed in a forced air drying oven at 90°C for 12-24 hours.

[0020] Preferably, the theoretical doping amount of phosphorus modification in step (5) is 1%.

[0021] Preferably, the specific steps are as follows:

[0022] (1) Loading the catalyst: Place a layer of quartz wool with a thickness of 10 mm in the middle of a quartz reaction tube with a diameter of 10 mm, add the catalyst into the reaction tube and ensure that the catalyst is flat, and then pad it with another layer of quartz wool with a thickness of 10 mm.

[0023] (2) Before the reaction: The entire pipeline was heated at 20 mL / min N 2 The system was purged with a flow rate of 60 min to remove air and moisture from the system. At the same time, the temperature was controlled to rise to 150°C at 5°C / min and maintained for 30 min, and then to 180°C at 5°C / min. Then, HCl was introduced at a flow rate of V = 20 mL / min and maintained for 30 min, and then V (C 2 H 2 ) =16 mL / min, V(HCl) =16.8 mL / min was introduced into the reaction gas and maintained for 10 min to ensure that the catalyst was in the gas atmosphere of acetylene and hydrogen chloride, and then V(C 2 H 2 ) / V(HCl)=1:1.05, and then maintain the reaction flow rate for ten minutes before starting online detection.

[0024] (3) After the reaction: The gaseous product is first passed through an absorption bottle containing NaOH solution to remove excess HCl, and then analyzed online by gas chromatography to evaluate the acetylene conversion rate and selectivity for vinyl chloride.

[0025] Beneficial effects:

[0026] The present invention provides a high-stability copper-based catalyst for acetylene hydrochlorination reaction and its preparation and application. Compared with other methods, this method greatly improves the stability of the copper-based catalyst during the acetylene hydrochlorination reaction and solves the problem of its easy deactivation. The technical solution adopted by the present invention is: the copper-based catalyst is modified by P3 = diethyl p-toluenesulfonyloxymethylphosphonate phosphorus modifier, anhydrous ethanol is selected as the solvent, and commercial activated carbon is used as the carrier to prepare a high-stability copper-based catalyst. The use of copper metal effectively saves production costs compared to precious metals such as gold and ruthenium; and the introduction of the phosphorus modifier inhibits the deactivation of the copper-based catalyst during the acetylene hydrochlorination reaction, and has excellent stability.

[0027] (1) The catalyst uses a phosphorus-containing ligand as a modifier, copper as the main active component, and anhydrous ethanol as a solvent. Through reasonable screening, the optimal conditions are 9% copper loading, 1% phosphorus doping, and 900°C calcination temperature. Improving the synthesis steps improves the performance of the catalyst.

[0028] (2) Modifier used in the present invention: by screening P1 = hydroxyethylidene diphosphonic acid, P2 = ethylenediaminetetramethylenephosphonic acid, P3 = p-toluenesulfonyloxymethylphosphonic acid diethyl ester, P4 = melamine phosphate, P5 = aminotrimethylenephosphonic acid = several as phosphorus modifiers, preferably P3 = p-toluenesulfonyloxymethylphosphonic acid diethyl ester as the modifier. Under the same conditions, the introduction of phosphorus-containing ligands forms a stable coordination bond with the active Cu species, thereby helping to stabilize the active copper species. After loading on the activated carbon, the active copper species is further calcined to stably anchor the active copper species on the surface of the activated carbon, thereby improving the catalytic stability and activity. Through a large number of experiments, the modifier used in the present invention is preferably p-toluenesulfonyloxymethylphosphonic acid diethyl ester. When the copper loading is 9%, under the conditions of reaction gas space velocity of 170h-1, V(C2H2) / V(HCl)=1:1.05 and reaction temperature of 180℃, the acetylene conversion rate can reach 71%, the vinyl chloride selectivity is greater than 99%, and the activity remains basically unchanged within 7.5h.

[0029] Compared with the prior art: first, the modifier selected in the present invention is non-toxic and harmless, and the price is low; second, the amount of modifier used in the present invention is small, and the utilization rate is high, so the modification cost is lower than other technologies. In short, the method of the present invention promotes the distribution of active copper species on activated carbon through the interaction between phosphorus-containing ligands and active copper species, and further anchors the active copper species on the surface of activated carbon through roasting, thereby enhancing the stability of the catalyst. The synthesis method in this technology can show excellent catalytic stability and can be used as an industrial application.

[0030] (3) Weigh 0.476 g of diethyl p-toluenesulfonyloxymethylphosphonate and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir with a magnetic stirrer at 350 rpm at room temperature for 30 min to obtain an ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate.

[0031] Weigh 1.107 g of cupric chloride dihydrate in step (2), pour it into the above-mentioned ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate, stir at room temperature for 5 h with a magnetic stirrer at 350 rpm to obtain a mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate;

[0032] In step (3), 3 g of activated carbon was weighed using an electronic balance and poured into the mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate, and stirred at room temperature for 24 h with a magnetic stirrer at 350 rpm. The mass ratio of copper in the catalyst: phosphorus in the modifier: carrier was 9:1:90.

[0033] In step (4), the catalyst is placed in a forced air drying oven and dried for 12-24 hours;

[0034] Step (5) The dried catalyst is placed in a tubular furnace, the nitrogen flow rate is maintained at 20 mL / min, the temperature is raised to 900°C at a heating rate of 5°C / min, and calcined for 1 h to obtain a phosphorus-modified copper-based catalyst 9%Cu / P3AC-900°C (1%P); wherein the 9%Cu / P3AC-900°C (1%P) catalyst is heated at an acetylene space velocity of 170 h -1 At T = 180 ° C, the conversion rate of acetylene is 71%, the selectivity of vinyl chloride is 99%, and the activity remains basically unchanged within 7.5 hours.

[0035] (4) Figure 1 That is, comparative examples 3, 4, and 5 explored the effect of copper loading on catalytic performance, among which 15%Cu / P3AC-900℃ had the best activity of 73.4%, but its activity was only 2.4% higher than that of 9%Cu / P3AC-900℃ catalyst. Considering that its higher loading has no economic value, 9%Cu / P3AC-900℃ is still considered to be the best catalyst. Figure 2 That is, comparative examples 2, 3, 4, and 5 explored the effects of different phosphorus sources on catalytic performance. The introduction of all phosphorus sources improved the catalytic activity, among which P3 had the best activity as the phosphorus source. Figure 3 That is, comparative examples 10, 11, and 12 explored the effect of phosphorus doping amount on catalytic performance. As the phosphorus doping amount increased, the activity increased, but obvious deactivation occurred. Figure 4 That is, comparative examples 6, 7, 8, and 9 explored the effect of calcination temperature on catalytic performance. As the calcination temperature increased, the catalytic activity showed a volcanic type. Among them, the catalytic activity of the 9%Cu / P3AC-900℃(1%) catalyst in Example 1 was the best. Under the conditions of acetylene space velocity of 170h-1 and T=180℃, the conversion rate of acetylene was 71%, the selectivity of vinyl chloride was 99%, and no deactivation occurred within 7.5h. The conversion rate of the 9%Cu / AC catalyst dropped from the initial 61.2% to 54.7% in the reaction of 7.5h, and the conversion rate of the 9%Cu / AC-900℃ catalyst was only 52.8%, indicating that the introduction of the phosphorus modifier enhanced the catalytic activity and stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The present invention will be further described below in conjunction with the accompanying drawings.

[0037] Figure 1 The relationship between acetylene conversion rate and reaction time of copper-based catalysts with different copper loadings.

[0038] Figure 2 The relationship between acetylene conversion and reaction time of copper-based catalysts modified with different phosphorus modifiers.

[0039] Figure 3The relationship between acetylene conversion rate and reaction time of copper-based catalysts with different phosphorus doping amounts.

[0040] Figure 4 The relationship between acetylene conversion and reaction time of copper-based catalysts calcined at different temperatures.

[0041] Figure 5 XRD patterns of copper-based catalysts calcined at different temperatures. DETAILED DESCRIPTION

[0042] Example 1 Catalyst Preparation

[0043] (1) Weigh 0.476 g of diethyl p-toluenesulfonyloxymethylphosphonate and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir the mixture at 350 rpm with a magnetic stirrer at room temperature for 30 min to obtain an ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate.

[0044] (2) Weigh 1.107 g of cupric chloride dihydrate, pour it into the above-mentioned ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate, stir at room temperature for 5 h with a magnetic stirrer at 350 rpm to obtain a mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate;

[0045] (3) Using an electronic balance, 3 g of activated carbon was weighed and poured into the mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate. The mixture was stirred at 350 rpm on a magnetic stirrer at room temperature for 24 h. The mass ratio of copper in the catalyst: phosphorus in the modifier: carrier was 9:1:90.

[0046] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0047] (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 900°C at a heating rate of 5°C / min, and calcined for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0048] The catalyst was named 9%Cu / P3AC-900°C (1%P).

[0049] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are as follows:

[0050] 1. Loading the catalyst: Place a layer of quartz wool with a thickness of 10 mm in the middle of a quartz reaction tube with a diameter of 10 mm, add about 1.41 mL of catalyst into the reaction tube and ensure that the catalyst is flat, and then place another layer of quartz wool with a thickness of 10 mm;

[0051] 2. Before reaction: The whole pipeline was heated at 20 mL min−1 N 2 The system was purged at a flow rate of 60 min to remove air and moisture from the system. At the same time, the temperature was controlled to rise to 150 °C at 5 °C / min and maintained for 30 min, and then to 180 °C at 5 °C / min. Then, hydrogen chloride was introduced at a flow rate of V = 20 mL / min and maintained for 30 min, and then V (C 2 H 2 ) =16 mL / min, V(HCl) =16.8 mL / min was introduced into the reaction gas and maintained for 10 min to ensure that the catalyst was in the gas atmosphere of acetylene and hydrogen chloride, and then V(C 2 H 2 )=4ml / min, V(C 2 H 2 ) / V(HCl)=1:1.05, reduce the reaction gas flow rate, maintain it at the reaction flow rate for ten minutes, and then start detection;

[0052] 3. After the reaction: The gas phase product is first passed through an absorption bottle containing NaOH solution to remove excess HCl, and then analyzed online by gas chromatography to evaluate the acetylene conversion rate and selectivity to VCM.

[0053] Comparative Example 1

[0054] (1) Weigh 0.9549 g of cupric chloride dihydrate and pour it into 20 mL of ethanol solution. Stir with a magnetic stirrer at 350 rpm at room temperature for 30 min.

[0055] (2) Using an electronic balance, 3 g of activated carbon was weighed and poured into the above solution. The solution was stirred at 350 rpm using a magnetic stirrer at room temperature for 24 h. The mass ratio of copper to carrier in the catalyst was 9:91.

[0056] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0057] The catalyst was named 9%Cu / AC.

[0058] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are the same as those in Example 1 and will not be repeated here.

[0059] Comparative Example 2

[0060] (1) Weigh 0.9549 g of cupric chloride dihydrate and pour it into 20 mL of ethanol solution. Stir with a magnetic stirrer at 350 rpm at room temperature for 30 min.

[0061] (2) Using an electronic balance, 3 g of activated carbon was weighed and poured into the above solution. The solution was stirred at 350 rpm using a magnetic stirrer at room temperature for 24 h. The mass ratio of copper to carrier in the catalyst was 9:91.

[0062] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0063] (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 900°C at a heating rate of 5°C / min, and calcined for 1 h to obtain a calcined copper-based catalyst.

[0064] The catalyst was named 9%Cu / AC-900°C.

[0065] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are the same as those in Example 1 and will not be repeated here.

[0066] Comparative Example 3

[0067] (1) Weigh 0.376 g of diethyl p-toluenesulfonyloxymethylphosphonate and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir the mixture at 350 rpm with a magnetic stirrer at room temperature for 30 min to obtain an ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate.

[0068] (2) Weigh 0.6476 g of cupric chloride dihydrate, pour it into the above-mentioned ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate, stir at room temperature for 5 h with a magnetic stirrer at 350 rpm to obtain a mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate;

[0069] (3) Using an electronic balance, 3 g of activated carbon was weighed and poured into the mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate. The mixture was stirred at 350 rpm on a magnetic stirrer at room temperature for 24 h. The mass ratio of copper in the catalyst: phosphorus in the modifier: carrier was 6:1:93.

[0070] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0071] (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 900°C at a heating rate of 5°C / min, and calcined for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0072] The catalyst was named 6%Cu / P3AC-900°C (1%P).

[0073] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are the same as those in Example 1 and will not be repeated here.

[0074] Comparative Example 4

[0075] (1) Weigh 0.48 g of diethyl p-toluenesulfonyloxymethylphosphonate and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir the mixture at 350 rpm with a magnetic stirrer at room temperature for 30 min to obtain an ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate.

[0076] (2) Weigh 1.652 g of cupric chloride dihydrate, pour it into the above-mentioned ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate, stir at room temperature for 5 h with a magnetic stirrer at 350 rpm to obtain a mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate;

[0077] (3) Using an electronic balance, 3 g of activated carbon was weighed and poured into the mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate. The mixture was stirred at 350 rpm on a magnetic stirrer at room temperature for 24 h. The mass ratio of copper in the catalyst: phosphorus in the modifier: carrier was 12:1:87.

[0078] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0079] (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 900°C at a heating rate of 5°C / min, and calcined for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0080] The catalyst was named 12%Cu / P3AC-900°C (1%P).

[0081] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are the same as those in Example 1 and will not be repeated here.

[0082] Comparative Example 5

[0083] (1) Weigh 0.556 g of diethyl p-toluenesulfonyloxymethylphosphonate and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir the mixture at 350 rpm with a magnetic stirrer at room temperature for 30 min to obtain an ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate.

[0084] (2) Weigh 2.394 g of cupric chloride dihydrate, pour it into the above-mentioned ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate, stir at room temperature for 5 h with a magnetic stirrer at 350 rpm to obtain a mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate;

[0085] (3) Using an electronic balance, 3 g of activated carbon was weighed and poured into the mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate. The mixture was stirred at 350 rpm on a magnetic stirrer at room temperature for 24 h. The mass ratio of copper in the catalyst: phosphorus in the modifier: carrier was 15:1:84.

[0086] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0087] (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 900°C at a heating rate of 5°C / min, and calcined for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0088] The catalyst was named 15%Cu / P3AC-900°C (1%P).

[0089] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are the same as those in Example 1 and will not be repeated here.

[0090] Comparative Example 6

[0091] (1) Weigh 0.476 g of diethyl p-toluenesulfonyloxymethylphosphonate and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir the mixture at 350 rpm with a magnetic stirrer at room temperature for 30 min to obtain an ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate.

[0092] (2) Weigh 1.107 g of cupric chloride dihydrate, pour it into the above-mentioned ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate, stir at room temperature for 5 h with a magnetic stirrer at 350 rpm to obtain a mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate;

[0093] (3) Using an electronic balance, 3 g of activated carbon was weighed and poured into the mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate. The mixture was stirred at 350 rpm on a magnetic stirrer at room temperature for 24 h. The mass ratio of copper in the catalyst: phosphorus in the modifier: carrier was 9:1:90.

[0094] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0095] (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 600°C at a heating rate of 5°C / min, and calcined for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0096] The catalyst was named 9%Cu / P3AC-600°C (1%P).

[0097] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are the same as those in Example 1 and will not be repeated here.

[0098] Comparative Example 7

[0099] (1) Weigh 0.476 g of diethyl p-toluenesulfonyloxymethylphosphonate and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir the mixture at 350 rpm with a magnetic stirrer at room temperature for 30 min to obtain an ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate.

[0100] (2) Weigh 1.107 g of cupric chloride dihydrate, pour it into the above-mentioned ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate, stir at room temperature for 5 h with a magnetic stirrer at 350 rpm to obtain a mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate;

[0101] (3) Using an electronic balance, 3 g of activated carbon was weighed and poured into the mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate. The mixture was stirred at 350 rpm on a magnetic stirrer at room temperature for 24 h. The mass ratio of copper in the catalyst: phosphorus in the modifier: carrier was 9:1:90.

[0102] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0103] (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 700°C at a heating rate of 5°C / min, and the catalyst was calcined for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0104] The catalyst was named 9%Cu / P3AC-700°C (1%P).

[0105] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are the same as those in Example 1 and will not be repeated here.

[0106] Comparative Example 8

[0107] (1) Weigh 0.476 g of diethyl p-toluenesulfonyloxymethylphosphonate and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir the mixture at 350 rpm with a magnetic stirrer at room temperature for 30 min to obtain an ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate.

[0108] (2) Weigh 1.107 g of cupric chloride dihydrate, pour it into the above-mentioned ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate, stir at room temperature for 5 h with a magnetic stirrer at 350 rpm to obtain a mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate;

[0109] (3) Using an electronic balance, 3 g of activated carbon was weighed and poured into the mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate. The mixture was stirred at 350 rpm on a magnetic stirrer at room temperature for 24 h. The mass ratio of copper in the catalyst: phosphorus in the modifier: carrier was 9:1:90.

[0110] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0111] (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 800°C at a heating rate of 5°C / min, and the catalyst was calcined for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0112] The catalyst was named 9%Cu / P3AC-800°C (1%P).

[0113] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are the same as those in Example 1 and will not be repeated here.

[0114] Comparative Example 9

[0115] (1) Weigh 0.476 g of diethyl p-toluenesulfonyloxymethylphosphonate and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir the mixture at 350 rpm with a magnetic stirrer at room temperature for 30 min to obtain an ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate.

[0116] (2) Weigh 1.107 g of cupric chloride dihydrate, pour it into the above-mentioned ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate, stir at room temperature for 5 h with a magnetic stirrer at 350 rpm to obtain a mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate;

[0117] (3) Using an electronic balance, 3 g of activated carbon was weighed and poured into the mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate. The mixture was stirred at 350 rpm on a magnetic stirrer at room temperature for 24 h. The mass ratio of copper in the catalyst: phosphorus in the modifier: carrier was 9:1:90.

[0118] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0119] (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 1000°C at a heating rate of 5°C / min, and the catalyst was calcined for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0120] The catalyst was named 9%Cu / P3AC-1000°C (1%P).

[0121] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are the same as those in Example 1 and will not be repeated here.

[0122] Comparative Example 10

[0123] (1) Weigh 1.1329 g of diethyl p-toluenesulfonyloxymethylphosphonate and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir the mixture at 350 rpm with a magnetic stirrer at room temperature for 30 min to obtain an ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate.

[0124] (2) Weigh 1.315 g of cupric chloride dihydrate, pour it into the above-mentioned ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate, stir at room temperature for 5 h with a magnetic stirrer at 350 rpm to obtain a mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate;

[0125] (3) Using an electronic balance, 3 g of activated carbon was weighed and poured into the mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate. The mixture was stirred at 350 rpm on a magnetic stirrer at room temperature for 24 h. The mass ratio of copper in the catalyst: phosphorus in the modifier: carrier was 9:2:89.

[0126] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0127] (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 900°C at a heating rate of 5°C / min, and calcined for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0128] The catalyst was named 9%Cu / P3AC-900°C (2%P).

[0129] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are the same as those in Example 1 and will not be repeated here.

[0130] Comparative Example 11

[0131] (1) Weigh 2.095 g of diethyl p-toluenesulfonyloxymethylphosphonate and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir with a magnetic stirrer at 350 rpm at room temperature for 30 min to obtain an ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate.

[0132] (2) Weigh 1.6217 g of cupric chloride dihydrate, pour it into the above-mentioned ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate, stir at room temperature for 5 h with a magnetic stirrer at 350 rpm to obtain a mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate;

[0133] (3) Using an electronic balance, 3 g of activated carbon was weighed and poured into the mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate. The mixture was stirred at 350 rpm on a magnetic stirrer at room temperature for 24 h. The mass ratio of copper in the catalyst: phosphorus in the modifier: carrier was 9:3:88.

[0134] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0135] (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 900°C at a heating rate of 5°C / min, and calcined for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0136] The catalyst was named 9%Cu / P3AC-900°C (3%P).

[0137] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are the same as those in Example 1 and will not be repeated here.

[0138] Comparative Example 12

[0139] (1) Weigh 3.642 g of diethyl p-toluenesulfonyloxymethylphosphonate and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir the mixture at 350 rpm with a magnetic stirrer at room temperature for 30 min to obtain an ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate.

[0140] (2) Weigh 2.114 g of cupric chloride dihydrate, pour it into the above-mentioned ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate, stir at room temperature for 5 h with a magnetic stirrer at 350 rpm to obtain a mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate;

[0141] (3) Using an electronic balance, 3 g of activated carbon was weighed and poured into the mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate. The mixture was stirred at 350 rpm on a magnetic stirrer at room temperature for 24 h. The mass ratio of copper in the catalyst: phosphorus in the modifier: carrier was 9:4:87.

[0142] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0143] (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 900°C at a heating rate of 5°C / min, and calcined for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0144] The catalyst was named 9%Cu / P3AC-900°C (4%P).

[0145] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are the same as those in Example 1 and will not be repeated here.

[0146] Example 2

[0147] (1) Weigh 0.1374 g of hydroxyethylidene diphosphonic acid and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir with a magnetic stirrer at 350 rpm at room temperature for 30 min to obtain an ethanol solution of hydroxyethylidene diphosphonic acid.

[0148] (2) Weigh 0.998 g of cupric chloride dihydrate and pour it into the above ethanol solution of hydroxyethylidene diphosphonic acid. Stir with a magnetic stirrer at 350 rpm at room temperature for 5 h to obtain a mixed solution of hydroxyethylidene diphosphonic acid and cupric chloride dihydrate.

[0149] (3) Using an electronic balance, 3 g of activated carbon was weighed and poured into the mixed solution of hydroxyethylidene diphosphonic acid and cupric chloride dihydrate. The mixture was stirred at 350 rpm on a magnetic stirrer at room temperature for 24 h. The mass ratio of copper in the catalyst: phosphorus in the modifier: carrier was 9:1:90.

[0150] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0151] (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 900°C at a heating rate of 5°C / min, and calcined for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0152] The catalyst was named 9%Cu / P1AC-900°C (1%P).

[0153] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are the same as those in Example 1 and will not be repeated here.

[0154] Example 3

[0155] (1) Weigh 0.1458 g of EDTP and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir with a magnetic stirrer at 350 rpm at room temperature for 30 min to obtain an ethanol solution of EDTP.

[0156] (2) Weigh 1 g of cupric chloride dihydrate and pour it into the above-mentioned ethylenediaminetetramethylenephosphoric acid ethanol solution. Stir with a magnetic stirrer at 350 rpm at room temperature for 5 h to obtain a mixed solution of ethylenediaminetetramethylenephosphoric acid and cupric chloride dihydrate.

[0157] (3) Using an electronic balance, 3 g of activated carbon was weighed and poured into the mixed solution of ethylenediaminetetramethylenephosphoric acid and cupric chloride dihydrate. The mixture was stirred at 350 rpm on a magnetic stirrer at room temperature for 24 h. The mass ratio of copper in the catalyst: phosphorus in the modifier: carrier was 9:1:90.

[0158] (4) Dry the above catalyst in a forced air drying oven for 12-24 hours;

[0159] (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 900°C at a heating rate of 5°C / min, and calcined for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0160] The catalyst was named 9%Cu / P2AC-900°C (1%P).

[0161] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are the same as those in Example 1 and will not be repeated here.

[0162] Example 4

[0163] (1) Weigh 0.207 g of melamine phosphate and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir with a magnetic stirrer at 350 rpm at room temperature for 30 min to obtain an ethanol solution of melamine phosphate.

[0164] (2) Weigh 1.02 g of cupric chloride dihydrate, pour it into the above melamine phosphate ethanol solution, stir at room temperature for 5 h with a magnetic stirrer at 350 rpm to obtain a mixed solution of melamine phosphate and cupric chloride dihydrate;

[0165] (3) Weigh 3 g of activated carbon using an electronic balance and pour it into the above-mentioned mixed solution of melamine phosphate and copper dichloride dihydrate. Stir with a magnetic stirrer at 350 rpm for 24 h at room temperature. The mass ratio of copper in the catalyst: phosphorus in the modifier: the mass of the carrier is 9:1:90.

[0166] (4) Place the above catalyst in a forced-air drying oven and dry it for 12 - 24 h;

[0167] (5) Place the dried catalyst in a tubular furnace, keep the nitrogen flow rate at 20 mL / min, and heat it to 900 °C at a heating rate of 5 °C / min and calcine for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0168] The catalyst is named 9%Cu / P4AC-900 °C(1%P).

[0169] The steps for using the phosphorus-modified copper-based catalyst in the fixed-bed acetylene hydrochlorination to produce vinyl chloride reaction are the same as those in Example 1 and will not be repeated here.

[0170] Example 5

[0171] (1) Weigh 0.133 g of aminotrimethylene phosphonic acid, place it in a beaker containing 20 ml of absolute ethanol for dispersion, stir with a magnetic stirrer at 350 rpm for 30 min at room temperature to obtain an ethanol solution of aminotrimethylene phosphonic acid;

[0172] (2) Weigh 0.996 g of copper dichloride dihydrate, pour it into the above ethanol solution of aminotrimethylene phosphonic acid, stir with a magnetic stirrer at 350 rpm for 5 h at room temperature to obtain a mixed solution of aminotrimethylene phosphonic acid and copper dichloride dihydrate;

[0173] (3) Weigh 3 g of activated carbon using an electronic balance and pour it into the above-mentioned mixed solution of aminotrimethylene phosphonic acid and copper dichloride dihydrate. Stir with a magnetic stirrer at 350 rpm for 24 h at room temperature. The mass ratio of copper in the catalyst: phosphorus in the modifier: the mass of the carrier is 9:1:90.

[0174] (4) Place the above catalyst in a forced-air drying oven and dry it for 12 - 24 h;

[0175] (5) Place the dried catalyst in a tubular furnace, keep the nitrogen flow rate at 20 mL / min, and heat it to 900 °C at a heating rate of 5 °C / min and calcine for 1 h to obtain a phosphorus-modified copper-based catalyst.

[0176] The catalyst is named 9%Cu / P5AC-900 °C(1%P).

[0177] The steps of using phosphorus-modified copper-based catalyst for fixed-bed acetylene hydrochlorination to produce vinyl chloride are the same as those in Example 1 and will not be repeated here.

[0178] Table 1 Acetylene hydrochlorination reaction activity test

[0179]

[0180]

[0181] Figure 1 That is, comparative examples 3, 4, and 5 explored the effect of copper loading on catalytic performance, among which 15%Cu / P3AC-900℃ had the best activity of 73.4%, but its activity was only 2.4% higher than that of 9%Cu / P3AC-900℃ catalyst. Considering that its higher loading has no economic value, 9%Cu / P3AC-900℃ is still considered to be the best catalyst. Figure 2 That is, comparative examples 2, 3, 4, and 5 explored the effects of different phosphorus sources on catalytic performance. The introduction of all phosphorus sources improved the catalytic activity, among which P3 had the best activity as the phosphorus source. Figure 3 That is, comparative examples 10, 11, and 12 explored the effect of phosphorus doping amount on catalytic performance. As the phosphorus doping amount increased, the activity increased, but obvious deactivation occurred. Figure 4 That is, comparative examples 6, 7, 8, and 9 explored the effect of calcination temperature on catalytic performance. As the calcination temperature increased, the catalytic activity showed a volcanic pattern. The catalytic activity of the 9%Cu / P3AC-900°C (1%) catalyst in Example 1 was optimal when the acetylene space velocity was 170 h -1 At T = 180 ° C, the conversion rate of acetylene was 71%, the selectivity of vinyl chloride was 99%, and no deactivation occurred within 7.5 hours. The conversion rate of the 9% Cu / AC catalyst dropped from the initial 61.2% to 54.7% in 7.5 hours of reaction, and the conversion rate of the 9% Cu / AC-900 ° C catalyst was only 52.8%, indicating that the introduction of the phosphorus modifier enhanced the catalytic activity and stability. Figure 5 Figure 2 XRD images of copper-based catalysts calcined at different temperatures. All catalysts have Cu diffraction peaks at 43.3°, 50.43° and 74.13°, corresponding to the (111), (200) and (220) crystal planes of Cu, respectively. This may be due to the reduction of some copper species under high-temperature calcination. It is worth noting that the diffraction peak of Cu3P appears at a calcination temperature of 900°C, indicating that Cu-P bonds are successfully generated at high temperatures. This may be the reason why 9%Cu / P3AC-900°C has the best activity.

Claims

1. A method for using a high-stability copper-based catalyst for acetylene hydrochlorination, characterized in that : The catalyst was used in the fixed-bed acetylene hydrochlorination reaction to produce vinyl chloride at an acetylene space velocity of 170 h -1 , V (C2H2) / V (HCl) =1:1.05, vinyl chloride is produced under the condition of reaction temperature of 180 ℃; The preparation method of the highly stable copper-based catalyst for acetylene hydrochlorination reaction comprises the following steps: (1) Weigh 0.476 g of diethyl p-toluenesulfonyloxymethylphosphonate and disperse it in a beaker containing 20 ml of anhydrous ethanol. Stir the mixture at 350 rpm with a magnetic stirrer at room temperature for 30 min to obtain an ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate. (2) Weigh 1.107 g of cupric chloride dihydrate, pour it into the above-mentioned ethanol solution of diethyl p-toluenesulfonyloxymethylphosphonate, stir at room temperature for 5 h with a magnetic stirrer at 350 rpm to obtain a mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate; (3) Weigh 3 g of activated carbon and pour it into the mixed solution of diethyl p-toluenesulfonyloxymethylphosphonate and cupric chloride dihydrate, stir at room temperature for 24 h with a magnetic stirrer at 350 rpm, and the mass ratio of copper in the catalyst: phosphorus in the modifier: carrier is 9:1:90; (4) Dry the above catalyst in a forced air drying oven for 12-24 hours; (5) The dried catalyst was placed in a tubular furnace, the nitrogen flow rate was maintained at 20 mL / min, the temperature was increased to 900°C at a heating rate of 5°C / min, and calcined for 1 h to obtain a phosphorus-modified copper-based catalyst.

2. The method for using the high stability copper-based catalyst for acetylene hydrochlorination according to claim 1 is characterized in that: In step (1), anhydrous ethanol is used as a solvent, and an appropriate amount of diethyl p-toluenesulfonyloxymethylphosphonate solid is dissolved in anhydrous ethanol at room temperature, and a magnetic stirrer is used to stir at 350 rpm for 30 min at room temperature.

3. The method for using the high stability copper-based catalyst according to claim 1 for acetylene hydrochlorination reaction, characterized in that The mass ratio of the copper in step (2) to the phosphorus in diethyl p-toluenesulfonyloxymethylphosphonate is 9:

1.

4. The method for using the high stability copper-based catalyst for acetylene hydrochlorination according to claim 1, characterized in that The activated carbon in step (3) is in the shape of column, powder or flake, with a particle size of 200 mesh and a specific surface area of ​​1000-1200m 2 / g.

5. The method for using the high stability copper-based catalyst for acetylene hydrochlorination according to claim 1, characterized in that The catalyst after stirring in step (4) should be placed in a 90°C forced air drying oven for 12-24 h.

6. The method for using the high stability copper-based catalyst for acetylene hydrochlorination according to claim 1, characterized in that : The theoretical doping amount of phosphorus modification in step (5) is 1% by mass.

7. The method for using the high stability copper-based catalyst for acetylene hydrochlorination according to claim 1, characterized in that: The specific steps are as follows: (1) Loading the catalyst: Place a layer of quartz wool with a thickness of 10 mm in the middle of a quartz reaction tube with a diameter of 10 mm, add 1.41 mL of catalyst into the reaction tube and ensure that the catalyst is flat, and then pad it with a layer of quartz wool with a thickness of 10 mm; (2) Before the reaction: The entire pipeline was purged with N2 at a flow rate of 20 mL / min for 60 min to remove air and moisture in the system. At the same time, the temperature was controlled to increase to 150 °C at 5 °C / min and maintained for 30 min, and then increased to 180 °C at 5 °C / min; then, HCl was introduced at a flow rate of V = 20 mL / min and maintained for 30 min, and then the reaction gas was introduced at a flow rate of V(C2H2) = 16 mL / min, V(HCl) = 16.8 mL / min and maintained for 10 min to ensure that the catalyst was in the gas atmosphere of acetylene and hydrogen chloride, and then the reaction gas flow rate was reduced to a ratio of V(C2H2) / V(HCl) = 1:1.

05. After maintaining the reaction flow rate for ten minutes, online detection began; (3) After the reaction: The gaseous product is first passed through an absorption bottle containing NaOH solution to remove excess HCl, and then analyzed online by gas chromatography to evaluate the acetylene conversion rate and selectivity for vinyl chloride.

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