A resin-based catalyst, preparation method and application in the production of polyvinyl chloride

Abstract

The present invention relates to a resin-based catalyst, a preparation method and an application in the production of polyvinyl chloride. The bonding ability of the surface of the resin carrier is increased by high-temperature swelling, ionization treatment and other methods. When used as a catalyst carrier, the dispersion of the catalyst active sites can be improved to a certain extent, the interaction between metal ions and the carrier surface can be enhanced, the rate at which the metal ions are reduced can be greatly slowed down, and the adsorption of hydrogen chloride can be enhanced, and the carbon deposition phenomenon on the catalyst surface can be reduced. A non-carbonized functional resin carrier is provided, and the research scope of metal catalysts is expanded from conventional carbon material loading systems to non-carbonized functional polymer systems. Catalysts based on resin-based carriers show higher stability and catalytic activity.

Description

Technical Field

[0001] The invention belongs to the field of catalysts containing gold, and in particular relates to a method for preparing a resin-based carrier catalyst and application of the catalyst in the production of polyvinyl chloride. Background Art

[0002] Polyvinyl chloride (PVC) is one of the world's top five general-purpose plastics. Its synthesis process is mainly based on the polymerization of vinyl chloride monomer (VCM). Due to the energy structure of "poor oil, rich coal and little gas", more than 80% of the domestic VCM monomer production process is currently mainly based on the "calcium carbide method", that is, the acetylene hydrochlorination process (C2H2+HCl=C2H5Cl) using a coal-based route. However, this process requires the use of a catalyst with mercuric chloride as the active component. Mercury-based catalysts seriously threaten ecological and environmental safety and human health due to their high toxicity and volatility.

[0003] Based on this, it is urgent to develop an efficient, stable, and environmentally friendly mercury-free catalyst and its related technology. In existing reports, mercury-free catalysts for acetylene hydrochlorination reactions mainly focus on precious metal-based catalysts represented by Au, Pd, Ru, etc., non-precious metal-based catalysts represented by Cu, Sn, Bi, etc., and metal-free catalysts represented by nitrogen-doped carbon materials. From the current industrial application experiments, gold-based catalysts have the potential to replace mercury-based catalysts from both technical and economic perspectives to meet the needs of large-scale use in acetylene hydrochlorination reactions. The most common gold-based catalyst preparation process reported in existing reports is to use activated carbon as a catalyst carrier to load gold nanoparticles. By changing the preparation process of gold-based catalysts, introducing suitable ligands, and introducing other metals to regulate the active sites on the catalyst surface to improve the activity and stability of gold-based catalysts, and extend the service life of gold-based catalysts, the purpose of reducing costs can be achieved. In addition, research on this type of catalyst also includes carbon material modification, nitrogen doping, or other metal doping. However, there are very few reports on resins as catalyst carriers for acetylene hydrochlorination reactions. Patent (111346663.A) discloses an amino resin modified nitrogen-doped activated carbon for use in acetylene hydrochlorination. Patent (117563667.A) prepares a gold-polymer catalyst by mixing gold-containing salts and polymers in a solvent; the catalyst itself has nitrogen and oxygen heteroatoms and a pore structure, which can provide anchoring points for the active center, weaken the self-agglomeration of the catalyst itself, and inhibit the loss and reduction of the active components of the catalyst in the acetylene hydrochlorination reaction. Patent (117816238.A) uses polyethylene nanofibers as a carrier to load gold-ionic liquids to prepare a catalyst with excellent stability. The polymer nanofibers can promptly conduct the heat generated by the catalyst during use to protect the high valence state of the metal and prevent the denaturation and loss of the ionic liquid.

[0004] At present, the main problems of catalysts using resin as carrier are that the active components are easy to fall off, the active sites are unevenly distributed, and the stability of the resin carrier is relatively poor. How to stabilize the active components on the surface of the resin carrier and prevent them from falling off during the reaction is a major problem in the preparation of resin-based catalysts at this stage. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a resin-based catalyst, a preparation method and application in the production of polyvinyl chloride.

[0006] The technical scheme adopted by the present invention is: a method for preparing a resin-based carrier, heating the resin at 40-60°C for expansion treatment, adding a reagent B containing a heterocyclic structure, and reflux reaction at 80-110°C; then adding benzyl chloride and reflux reaction at 80-110°C, and obtaining a modified resin-based carrier after secondary grafting modification.

[0007] Preferably, an inorganic salt solution reagent C capable of adjusting the pH value of the reaction system is added to the resin solution together with the reagent B;

[0008] Reagent B is one or more of imidazole, pyrazole, pyrrole, furan, thiazole, oxazole, pyrazine, pyridazine, pyridine and pyrimidine;

[0009] Reagent C is one or more of anhydrous sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium carbonate, calcium carbonate, magnesium carbonate, potassium sulfate, magnesium sulfate, calcium sulfate, sodium sulfate, and sodium bisulfate;

[0010] The mass ratio of resin: reagent B: reagent C: benzyl chloride is 1: 0.3–0.8: 0.3–0.8: 1.1–1.9.

[0011] Preferably, before the resin is modified, the resin is first purged with flowing nitrogen at a temperature of 60-80°C and then ultrasonically treated in deionized water.

[0012] Preferably, the resin is a combination of one or more resins having a basic skeleton of polystyrene, polyphenylene sulfide, polyaryletherketone, polyetherimide, polyimide, polytetrafluoroethylene, polycarbonate, polybenzimidazole, polyamideimide, polyphenylene sulfone, and polysulfone.

[0013] Preferably, the specific steps are as follows:

[0014] Step 1: Purge the resin with flowing nitrogen at a temperature of 60–80 °C for 6–10 h, with a nitrogen gas volume space velocity of 40–80 h –1 Then, the resin was placed in 8–10 times the volume of deionized water, and ultrasonically treated for at least 1 h before filtration and drying;

[0015] Step 2: placing the treated resin in the first dose of organic solvent A, heating to 40-60 °C for swelling treatment for 12-48 h, then adding reagent B and reagent C, reflux at 80-110 °C for 12-24 h, filtering, adding 1-3 times the volume of the first dose of organic solvent A and heating to 40-60 °C, adding benzyl chloride, reflux at 80-110 °C for 12-24 h, filtering and drying to obtain the modified resin;

[0016] The organic solvent A is a combination of one or more of acetonitrile, tetrahydrofuran, methanol, toluene, ethylbenzene, chloroform, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, ethyl acetate, dioxane, and petroleum ether; and the mass ratio of the resin to the first dose of organic solvent A is 1:8-43.

[0017] The invention relates to a resin-based carrier prepared by a method for preparing the resin-based carrier.

[0018] A resin-based catalyst used in the production of polyvinyl chloride is obtained by impregnating a noble metal salt into a resin-based carrier.

[0019] Preferably, the specific preparation process is as follows:

[0020] Step 3: Soak the resin-based carrier in 3-5 times the volume of organic solvent A at 40-60 °C for at least 2 hours, then add precious metal salt, reflux at 80-110 °C for 4-16 hours, filter, wash with organic solvent A, and dry to obtain a resin-based catalyst; wherein the precious metal salt accounts for 0.1%-2.5% of the mass of the modified resin;

[0021] The noble metal salt is a combination of one or more of gold chloride, palladium chloride, ruthenium chloride and platinum chloride.

[0022] The use of resin-based catalysts in the preparation of polyvinyl chloride.

[0023] Preferably, the method for using the resin-based catalyst to produce polyvinyl chloride monomer in a laboratory comprises the following steps:

[0024] The catalyst was loaded into a fixed-bed reactor for the synthesis of polyvinyl chloride monomer and pretreated at 150–200 °C under flowing nitrogen for at least 1 h.

[0025] Switch nitrogen to HCl and purge for at least 1 h; turn on C2H2 and set its gas space velocity to 80–320 h –1 , ensure that the volume ratio of HCl / C2H2 is 1.05–1.30:1;

[0026] The reaction tail gas is absorbed by alkaline solution and dehydrated by silica gel column before entering into gas chromatography for online analysis;

[0027] After the reaction is completed, turn off the raw gas first, then continue to purge with nitrogen for 0.5-1 h, and turn off the nitrogen after the temperature drops below 50 °C;

[0028] or,

[0029] The method for using a resin-based catalyst in the production of industrial polyvinyl chloride comprises the following steps:

[0030] The catalyst was loaded into an industrial polyvinyl chloride monomer synthesis unit and pretreated at 150–200 °C under flowing nitrogen for at least 48 h;

[0031] Switch nitrogen to HCl, purge for at least 12 h, then switch to HCl / C2H2 feed gas to start the reaction, and set the C2H2 gas space velocity to 10–60 h –1 , where the volume ratio of HCl / C2H2 is 1.05–1.30:1;

[0032] The polyvinyl chloride monomer produced by the reaction directly enters the subsequent polymerization unit for the synthesis of polyvinyl chloride, and the operation process of other units remains unchanged;

[0033] After the reaction is completed, the raw gas is first turned off, and then nitrogen is continued to be purged for at least 24 hours before cooling down. After the temperature drops to ambient temperature, the nitrogen is continued to be purged for at least 48 hours before turning off the nitrogen.

[0034] The advantages and positive effects of the present invention are: providing a method for modifying resin, grafting the resin skeleton structure by high-temperature swelling and ionization treatment, increasing the bonding ability of the resin carrier surface, improving the dispersibility of the catalyst active sites to a certain extent, enhancing the interaction force between the metal ions and the carrier surface, greatly slowing down the rate at which the metal ions are reduced, and enhancing the adsorption of hydrogen chloride;

[0035] With the help of Cl – Due to the coordination effect of anions, metal species can be dispersed rapidly at the atomic level. In addition, due to the higher coordination environment and stronger metal-support interaction, compared with conventional activated carbon-supported catalysts, MCl x / AC, [MCl x+n ] n– The stability of the catalytic system in the acetylene hydrochlorination reaction can be significantly improved;

[0036] Non-carbonized functional resin carriers and mild metal loading schemes are used in acetylene hydrochlorination reactions, expanding the research scope of metal catalysts from conventional carbon material loading systems to non-carbonized functional polymer systems, bringing great convenience to catalyst design and mechanism research; in addition, compared with carbon material carriers, the synthesis of resin-based carriers is controllable, easy to increase production, and suitable for industrial promotion. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 is a scanning electron microscope image of the CAT-1 catalyst prepared in Example 1. DETAILED DESCRIPTION

[0038] The embodiments of the present invention are described below with reference to the accompanying drawings.

[0039] The present invention relates to a resin-based catalyst, a preparation method and an application in the production of polyvinyl chloride. The bonding ability of the resin carrier surface is increased by high-temperature swelling, ionization treatment and other methods; when used as a catalyst carrier, the dispersion of the catalyst active sites can be improved to a certain extent, the interaction between metal ions and the carrier surface can be enhanced, the rate at which the metal ions are reduced can be greatly slowed down, and the adsorption of hydrogen chloride can be enhanced, and the carbon deposition phenomenon on the catalyst surface can be reduced. + cation (imidazolium cation) and Cl – The anion functionalizes the resin and uses Cl – Due to the coordination effect of anions, metal species can be quickly dispersed at the atomic level, expanding the research scope of metal catalysts from conventional carbon material loading systems to non-carbonized functional polymer systems.

[0040] First, the resin is modified to make it suitable for use as a carrier. The specific steps are as follows:

[0041] Step 1: Purge the resin with flowing nitrogen at a temperature of 60–80 °C for 6–10 h, with a nitrogen gas volume space velocity of 40–80 h –1 , then put the resin into 8-10 times the volume of deionized water, treat it under ultrasonic conditions for at least 1 hour, then filter and dry it to obtain the treated resin; through such treatment, the resin is cleaned, the foreign matter remaining in the resin structure is removed, the skeleton structure of the resin is retained, and the modification of the resin structure is facilitated;

[0042] Step 2: placing the cleaned resin in a first dose of organic solvent A, heating to 40-60 °C for swelling treatment for 12-48 h; wherein the organic solvent A is one or more of acetonitrile, tetrahydrofuran, methanol, toluene, ethylbenzene, chloroform, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, ethyl acetate, dioxane, and petroleum ether;

[0043] Add reagent B and reagent C to the expanded resin, then heat to 80-110 °C and reflux for 12-24 hours, and filter after cooling to room temperature; wherein reagent B has a heterocyclic structure, the purpose of which is to introduce more modifiable sites to facilitate subsequent grafting of more metal ions, and specifically can be a combination of one or more of imidazole, pyrazole, pyrrole, furan, thiazole, oxazole, pyrazine, pyridazine, pyridine, and pyrimidine; reagent C is an inorganic salt, the purpose of which is to adjust the pH of the reaction system to facilitate accelerating the reaction equilibrium, and specifically can be a combination of one or more of anhydrous sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium carbonate, calcium carbonate, magnesium carbonate, potassium sulfate, magnesium sulfate, calcium sulfate, sodium sulfate, and sodium bisulfate;

[0044] Then, 1-3 times the volume of the first dose of organic solvent A is added and heated to 40-60°C, and then benzyl chloride is added thereto and refluxed at 80-110°C for 12-24 hours. After cooling to room temperature, the mixture is filtered and dried to obtain a modified resin, which can be used as a catalyst carrier;

[0045] The mass ratio of resin: first dose organic solvent A: reagent B: reagent C: benzyl chloride is 1: 8–43: 0.3–0.8: 0.3–0.8: 1.1–1.9.

[0046] Through the above modification method, the functional groups in reagent B are sequentially grafted onto the resin skeleton, and then the benzyl group is grafted onto the functional group, thereby realizing the modification of the resin structure. The modified resin structure increases the metal sites, which can improve the anchoring ability between the catalyst metal sites and the resin carrier, thereby strengthening the interaction between the metal and the carrier, thereby changing the catalytic performance.

[0047] The modified resin is loaded with metal to prepare a catalyst, and the specific steps are as follows:

[0048] Step 3: At a temperature of 40-60 °C, soak the modified resin prepared in step 2 in 3-5 times the volume of organic solvent A for at least 2 h, then add precious metal salt, and reflux at 80-110 °C for 4-16 h, then filter the product at 80-110 °C, wash it three times with 3-5 times the volume of organic solvent A, and then dry it to obtain a resin-based catalyst; wherein the precious metal salt is one or more of gold chloride, palladium chloride, ruthenium chloride, and platinum chloride; wherein the precious metal salt accounts for 0.1%-2.5% of the mass of the modified resin.

[0049] By [Imiazolium] + Cations and Cl – The anion transforms the resin into an ion functionalized polymer. After the metal chloride salt is introduced, the metal ion will be converted into an ion functionalized polymer by the Cl – Further coordination generates [MClx+n ] n– The metal anion center is firmly anchored in the polymer system through ionic bonding. – Due to the coordination effect of anions, metal species can be dispersed rapidly at the atomic level. In addition, due to the higher coordination environment and stronger metal-support interaction, compared with conventional activated carbon-supported catalysts, MCl x / AC, [MCl x+n ] n– The stability of the catalytic system can be significantly improved.

[0050] In certain embodiments of the present invention, the prepared resin-based catalyst can be used in laboratory or industrial acetylene hydrochlorination to prepare polyvinyl chloride, as follows:

[0051] The method for using the resin-based catalyst for producing polyvinyl chloride monomer in a laboratory comprises the following steps:

[0052] (1) The catalyst was loaded into a fixed bed reactor for the synthesis of polyvinyl chloride monomer and pretreated at 150–200 °C under flowing nitrogen for at least 1 h;

[0053] (2) Switch nitrogen to HCl and purge for at least 1 h; then turn on C2H2 and set its gas space velocity to 80–320 h –1 , while ensuring that the volume ratio of HCl / C2H2 is 1.05–1.30:1;

[0054] (3) The reaction tail gas is absorbed by alkaline solution and dehydrated by silica gel column before entering the gas chromatography for online analysis;

[0055] (4) After the reaction is completed, turn off the raw gas first, then continue to purge with nitrogen for 0.5-1 h, then cool down, and turn off the nitrogen after the temperature drops below 50 °C.

[0056] The method for using a resin-based catalyst in the production of industrial polyvinyl chloride, wherein the catalyst is applied to the production process of industrial polyvinyl chloride monomer, comprising the following steps:

[0057] (1) The catalyst was loaded into an industrial polyvinyl chloride monomer synthesis unit and pretreated at 150–200 °C under flowing nitrogen for at least 48 h;

[0058] (2) Switch nitrogen to HCl, purge for at least 12 h, then switch to HCl / C2H2 feed gas to start the reaction, and set the C2H2 gas space velocity to 10–60 h –1 , where the volume ratio of HCl / C2H2 is 1.05–1.30:1;

[0059] (3) The polyvinyl chloride monomer produced by the reaction directly enters the subsequent polymerization unit for the synthesis of polyvinyl chloride, and the operating procedures of other units remain unchanged;

[0060] (4) After the reaction is completed, turn off the raw gas first, then continue to purge with nitrogen for at least 24 hours before cooling down. After the temperature drops to ambient temperature, continue to purge for at least 48 hours before turning off the nitrogen.

[0061] The catalyst prepared by the non-carbonized functional resin carrier and mild metal loading scheme is used for acetylene hydrochlorination reaction, which expands the research scope of metal catalysts from conventional carbon material loading systems to non-carbonized functional polymer systems, bringing great convenience to catalyst design and mechanism research. Compared with carbon-based carrier catalysts, the synthesis process of resin-based catalysts is controllable. Compared with carbon-based catalysts directly prepared from natural carbon raw materials, it is easy to increase the catalyst yield and is more suitable for industrial promotion. In addition, carbon-based catalysts need to be calcined and formed, and catalysts obtained by calcining different batches are prone to differences. The preparation process of resin-based catalysts is mild and controllable, and it is easy to synthesize resin-based carriers with uniform quality, which is conducive to production promotion.

[0062] The scheme of the present invention is described below in conjunction with data, wherein the experimental methods without specific operating steps are all carried out in accordance with the corresponding product instructions, and the instruments, reagents, and consumables used in the examples can all be purchased from commercial companies unless otherwise specified.

[0063] Example 1

[0064] (1) The polystyrene resin was purged with flowing nitrogen at 80 °C for 8 h, with a nitrogen gas volume space velocity of 80 h –1 Then, the resin was placed in 8 times the volume of deionized water, treated under ultrasonic conditions for 1 h, and then filtered and dried to obtain the treated resin.

[0065] (2) The treated resin was placed in acetonitrile, heated to 60 °C for swelling treatment for 12 h, and then imidazole and anhydrous sodium carbonate were added thereto, and then the temperature was raised to 100 °C and refluxed for 12 h. After cooling to room temperature, the mixture was filtered. Then, 3 times the volume of acetonitrile was added and heated to 60 °C, and then benzyl chloride was added thereto and refluxed at 100 °C for 12 h. After cooling to room temperature, the mixture was filtered and dried to obtain a modified resin. The mass ratio of polystyrene resin: acetonitrile: imidazole: anhydrous sodium carbonate: benzyl chloride was 1:20:0.5:0.5:1.5.

[0066] (3) The modified resin was immersed in 4 volumes of acetonitrile at 60 °C for 2 h, and then gold chloride was added and refluxed at 100 °C for 16 h. The product was then hot filtered, washed three times with 4 volumes of acetonitrile and dried to obtain a resin-based catalyst; the gold chloride accounted for 0.1% of the mass of the modified resin, and the catalyst was named CAT-1.

[0067] The prepared catalyst was tested by scanning electrodes, and the test pictures are as follows: Figure 1 shown.

[0068] Example 2

[0069] The preparation steps of Example 2 are the same as those of Example 1, except that the polystyrene resin in step (1) is replaced by polyaryletherketone resin. The obtained catalyst is numbered CAT-2.

[0070] Example 3

[0071] The preparation steps of Example 3 are the same as those of Example 1, except that the imidazole in step (2) is replaced by pyrazole. The obtained catalyst is numbered CAT-3.

[0072] Example 4

[0073] The preparation steps of Example 4 are the same as those of Example 1, except that the acetonitrile in step (2) is replaced by acetone. The obtained catalyst is numbered CAT-4.

[0074] Example 5

[0075] The preparation steps of Example 5 are the same as those of Example 1, except that the anhydrous sodium carbonate in step (2) is replaced by potassium carbonate. The resulting catalyst is numbered CAT-5.

[0076] Comparative Example 1

[0077] The purpose is to compare with Example 1 to compare the effects of the resin-based carrier and the activated carbon carrier on the catalyst.

[0078] The preparation steps of Comparative Example 1 are the same as steps (2) and (3) of Example 1, except that the polystyrene resin selected in step (2) is replaced by activated carbon; the obtained catalyst is numbered CAT-6.

[0079] Comparative Example 2

[0080] The purpose is to compare with Example 1 to compare the effects of the resin-based support and the nitrogen-doped carbon support on the catalyst.

[0081] The preparation steps of Comparative Example 2 are the same as steps (2) and (3) of Example 1, except that the polystyrene resin selected in step (2) is replaced by boron nitride; the obtained catalyst is numbered CAT-7.

[0082] Comparative Example 3

[0083] The purpose is to compare with Example 1 to compare the effects of the resin-based support and the metal oxide support on the catalyst.

[0084] The preparation steps of Comparative Example 3 are the same as steps (2) and (3) of Example 1, except that the polystyrene resin selected in step (2) is replaced by titanium dioxide; the obtained catalyst is numbered CAT-8.

[0085] Comparative Example 4

[0086] The purpose is to compare with Example 1 to illustrate the effect of the addition of benzyl chloride in step (2) on the catalyst.

[0087] The preparation steps of Comparative Example 4 are the same as those of Example 1, except that the step of adding benzyl chloride in step (2) is removed; the obtained catalyst is numbered CAT-9.

[0088] Comparative Example 5

[0089] The purpose is to compare with Example 1 to illustrate the effect of the resin ionization treatment on the catalyst in step (2). The specific steps are as follows;

[0090] (1) The polystyrene resin was purged with flowing nitrogen at 80 °C for 8 h, with a nitrogen gas volume space velocity of 80 h –1 Then, the resin was placed in 8 times the volume of deionized water, treated under ultrasonic conditions for 1 h, and then filtered and dried to obtain the treated resin.

[0091] (2) The resin was immersed in 4 volumes of acetonitrile at 60 °C for 2 h, and then gold chloride was added and refluxed at 100 °C for 16 h. The product was then hot filtered, washed three times with 4 volumes of acetonitrile and dried to obtain a resin-based catalyst; the gold chloride accounted for 0.1% of the mass of the modified resin, and the catalyst was named CAT-10.

[0092] Comparative Example 6

[0093] The purpose is to compare with Example 1 to illustrate the effect of the hot filtration treatment in step (3) on the catalyst.

[0094] The preparation steps of Comparative Example 6 are the same as those of Example 1, except that the hot filtration treatment in step (3) is replaced by cold filtration treatment, specifically cooling to room temperature before filtration; the obtained catalyst is numbered CAT-11.

[0095] Example 6: Application of resin-based catalyst in the preparation of polyvinyl chloride by acetylene hydrochlorination

[0096] The catalysts prepared in Examples 1-5 and Comparative Examples 1-6 were tested for activity, and the specific methods and conditions were as follows:

[0097] (1) 2 mL of the catalyst was loaded into a fixed-bed reactor for the synthesis of polyvinyl chloride monomer and pretreated at 180 °C for 1 h under flowing nitrogen.

[0098] (2) Switch nitrogen to HCl and purge for 1 h; then turn on C2H2 and set its gas space velocity to 160 h –1 , while ensuring that the volume ratio of HCl / C2H2 is 1.1:1;

[0099] (3) The reaction tail gas is absorbed by alkaline solution and dehydrated by silica gel column before entering the gas chromatography for online analysis;

[0100] (4) After the reaction is completed, turn off the raw gas first, then continue to purge with nitrogen for 1 hour, then cool down, and turn off the nitrogen after the temperature drops below 50 °C.

[0101] The results of vinyl chloride selectivity, acetylene conversion rate (average data for 5-10 h reaction) of each group of catalysts, and the rate of decrease of vinyl chloride conversion rate per unit time of each group of catalysts in the reaction range of 5-10 h are shown in Table 1.

[0102] Table 1 Data of resin-based catalysts in acetylene hydrochlorination

[0103]

[0104] The results are shown in Table 1. The CAT-1 catalyst prepared by using ionized polystyrene resin as the catalyst carrier and the CAT-2 catalyst prepared by using ionized polyaryletherketone resin as the catalyst carrier achieved 99.58% and 99.62% in vinyl chloride selectivity, and 87.56% and 89.12% in acetylene conversion, respectively. In the reaction period of 5-10 h, the decrease rates of vinyl chloride conversion per unit time of the catalyst were 0.24% and 0.25%, respectively. Compared with activated carbon, boron nitride and titanium dioxide, the resin and the resin after ionization treatment are suitable for acetylene hydrochlorination reaction, and have achieved good activity among the current non-activated carbon carriers.

[0105] The embodiments of the present invention are described in detail above, but the contents described are only preferred embodiments of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A method for preparing a resin-based carrier, characterized in that: The resin is heated at 40-60°C for expansion treatment, a reagent B containing a heterocyclic structure is added, and a reflux reaction is performed at 80-110°C; benzyl chloride is then added and a reflux reaction is performed at 80-110°C, and a modified resin-based carrier is obtained after secondary grafting modification.

2. The method for preparing a resin-based carrier according to claim 1, characterized in that: Adding an inorganic salt solution reagent C capable of adjusting the pH value of the reaction system together with the reagent B into the resin solution; Reagent B is one or more of imidazole, pyrazole, pyrrole, furan, thiazole, oxazole, pyrazine, pyridazine, pyridine and pyrimidine; Reagent C is one or more of anhydrous sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium carbonate, calcium carbonate, magnesium carbonate, potassium sulfate, magnesium sulfate, calcium sulfate, sodium sulfate, and sodium bisulfate; The mass ratio of resin: reagent B: reagent C: benzyl chloride is 1: 0.3–0.8: 0.3–0.8: 1.1–1.

9.

3. The method for preparing a resin-based carrier according to claim 1, characterized in that: Prior to resin modification, the resin was purged with flowing nitrogen at 60–80 °C and then sonicated in deionized water.

4. The method for preparing a resin-based carrier according to claim 1, characterized in that: The resin is a combination of one or more resins having a basic skeleton of polystyrene, polyphenylene sulfide, polyaryletherketone, polyetherimide, polyimide, polytetrafluoroethylene, polycarbonate, polybenzimidazole, polyamideimide, polyphenylene sulfone, and polysulfone.

5. The method for preparing a resin-based carrier according to claim 2, characterized in that: The specific steps are as follows: Step 1: Purge the resin with flowing nitrogen at a temperature of 60–80 °C for 6–10 h, with a nitrogen gas volume space velocity of 40–80 h –1 Then, the resin was placed in 8–10 times the volume of deionized water, and ultrasonically treated for at least 1 h before filtration and drying; Step 2: Place the treated resin in the first dose of organic solvent A, heat to 40-60 ° C for swelling treatment for 12-48 hours, then add reagent B and reagent C, reflux at 80-110 ° C for 12-24 hours, filter, add 1-3 times the volume of the first dose of organic solvent A and heat to 40-60 ° C, add benzyl chloride, reflux at 80-110 ° C for 12-24 hours, filter and dry to obtain the modified resin; The organic solvent A is a combination of one or more of acetonitrile, tetrahydrofuran, methanol, toluene, ethylbenzene, chloroform, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, ethyl acetate, dioxane, and petroleum ether; and the mass ratio of the resin to the first dose of organic solvent A is 1:8-43.

6. The resin-based carrier prepared by the method for preparing the resin-based carrier according to any one of claims 1 to 5.

7. A resin-based catalyst for use in the production of polyvinyl chloride, characterized in that: The resin-based catalyst is obtained by impregnating the resin-based carrier as claimed in claim 6 with a noble metal salt.

8. The resin-based catalyst for polyvinyl chloride production according to claim 7, characterized in that: The specific preparation process is as follows: Step 3: Soak the resin-based carrier in 3-5 times the volume of organic solvent A at 40-60 °C for at least 2 h, then add precious metal salt, reflux at 80-110 °C for 4-16 h, filter, wash with organic solvent A, and dry to obtain a resin-based catalyst; wherein the precious metal salt accounts for 0.1%-2.5% of the mass of the modified resin; The noble metal salt is a combination of one or more of gold chloride, palladium chloride, ruthenium chloride and platinum chloride.

9. Use of the resin-based catalyst according to claim 7 or 8 in the preparation of polyvinyl chloride.

10. The use according to claim 9, characterized in that: The method for producing polyvinyl chloride monomer in a laboratory using a resin-based catalyst comprises the following steps: The catalyst was loaded into a fixed-bed reactor for the synthesis of polyvinyl chloride monomer and pretreated at 150–200 °C under flowing nitrogen for at least 1 h. Switch nitrogen to HCl and purge for at least 1 h; turn on C2H2 and set its gas space velocity to 80–320 h –1 , ensure that the volume ratio of HCl / C2H2 is 1.05–1.30:1; The reaction tail gas is absorbed by alkaline solution and dehydrated by silica gel column before entering into gas chromatography for online analysis; After the reaction is completed, turn off the raw gas first, then continue to purge with nitrogen for 0.5-1 h, and turn off the nitrogen after the temperature drops below 50 °C; or, The method for using a resin-based catalyst in the production of industrial polyvinyl chloride comprises the following steps: The catalyst was loaded into an industrial polyvinyl chloride monomer synthesis unit and pretreated at 150–200 °C under flowing nitrogen for at least 48 h. Switch nitrogen to HCl, purge for at least 12 h, then switch to HCl / C2H2 feed gas to start the reaction, and set the C2H2 gas space velocity to 10–60 h –1 , where the volume ratio of HCl / C2H2 is 1.05–1.30:1; The polyvinyl chloride monomer produced by the reaction directly enters the subsequent polymerization unit for the synthesis of polyvinyl chloride, and the operation process of other units remains unchanged; After the reaction is completed, the raw gas is first turned off, and then nitrogen is continued to be purged for at least 24 hours before cooling down. After the temperature drops to ambient temperature, the nitrogen is continued to be purged for at least 48 hours before turning off the nitrogen.

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