A composite metal organic framework catalyst for catalyzing the hydrochlorination of acetylene, preparation and application thereof

Abstract

A composite metal organic framework catalyst for catalyzing acetylene hydrochlorination reaction, comprising an active component, a carrier and a metal organic framework ligand; the catalyst uses activated carbon as the carrier and copper salt as the active component, by adding a synergistic metal and a metal organic framework ligand containing a lone pair of electrons and an electron-withdrawing group, the metal ion is centered and the ligand is coordinated with each other through self-assembly to form a three-dimensional connected pore network structure, which has a strong anchoring and dispersion effect on the metal ion, thereby improving the activity and thermal stability of the catalyst; the catalyst is used for acetylene hydrochlorination reaction, has the characteristics of good catalytic stability, high activity, low cost and simple preparation process, and has great industrial application prospect.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to a composite metal-organic framework catalyst for catalyzing the hydrochlorination reaction of acetylene, its preparation method, and its application. Background Technology

[0002] Polyvinyl chloride (PVC), the world's second-largest general-purpose resin and China's largest-capacity polymer material, is synthesized by free radical polymerization of vinyl chloride (VCM) under the action of an initiator. PVC resin is white, non-toxic, odorless, has high thermal stability, and good plasticity, making it widely used in industry, agriculture, and daily necessities, such as pipes, profiles, agricultural films, cable sheaths, toys, and flooring. In recent years, with the gradual acceleration of industrialization, PVC production capacity has shown a year-on-year upward trend. In 2024, China's PVC production capacity reached 29.11 million tons, accounting for more than 45% of global PVC production capacity, with a total industry output value exceeding 100 billion yuan.

[0003] The main production processes for VCM include: coal-based acetylene process, petroleum-based ethylene process, and natural gas-based ethane process. Due to my country's unique energy endowment of being rich in coal, poor in oil, and lacking in natural gas, the coal-based calcium carbide acetylene process is the primary route for VCM production. Currently, the coal-based calcium carbide acetylene process still uses activated carbon supported on highly toxic mercuric chloride as a catalyst. Because this reaction is strongly exothermic, mercury easily sublimates at high temperatures, causing catalyst deactivation and posing a serious threat to human health and the environment. Since 2013, the Chinese government has introduced a series of policies and regulations to gradually restrict and prohibit the mining of mercury and its use in industries such as PVC.

[0004] Current research and industrial applications of mercury-free catalysts mainly focus on precious metals such as Au and Ru, and non-precious metal catalysts such as Cu and Bi. Years of academic research and industrial verification have shown that Au-based catalysts exhibit the best performance. However, their high cost limits the large-scale application of gold-based catalysts in the low-value-added PVC industry. Non-precious metal Cu-based catalysts, on the other hand, offer advantages such as abundant reserves, low price, and lower toxicity. In 1994, Deng Guocai et al. developed a non-precious metal-based copper-containing catalyst, whose initial catalytic activity approached that of traditional mercury-based catalysts. However, due to the easy loss of its active components Sn and Bi, the catalyst's stability was poor. CN102380380A describes a catalyst using activated carbon as the catalyst support and one or more of the non-precious metals copper, nickel, bismuth, zinc, manganese, and molybdenum as the active components. Under GHSV(C2H2) = 100–200 h⁻¹ conditions, the initial acetylene conversion rate was only 56.6%, which is relatively low compared to current industrial mercury-based catalysts. In CN201010574802.5, a composite catalyst was prepared using 15%-30% (wt%) stannous chloride as the main active material and barium chloride, copper chloride and zinc chloride as auxiliary agents under ultrasonic and micro-positive pressure conditions. The activity and selectivity of the catalyst for vinyl chloride were improved, but tin still lost relatively quickly in the form of stannous tetrachloride. Although the auxiliary agents could play a certain role in reducing tin loss, the stability of the catalyst was still very poor.

[0005] Although extensive scientific research and industrial demonstrations have been conducted on mercury-free catalysts, they still face problems such as poor catalyst stability, low catalytic activity, high levels of byproducts during the reaction, and easy carbon deposition. Therefore, developing a green, energy-saving, and efficient mercury-free catalyst technology is of great strategic significance for the mercury-free transformation of the PVC industry. Summary of the Invention

[0006] To overcome the problems of existing technologies, this invention provides a composite metal-organic framework catalyst for the hydrochlorination of acetylene, its preparation method, and its applications. This catalyst has the potential for large-scale industrial application. The specific technical solution is as follows:

[0007] On one hand, the present invention provides a composite metal-organic framework catalyst for catalyzing the hydrochlorination reaction of acetylene, comprising an active component, a metal-organic framework ligand, and a support. The active component includes a necessary active component copper salt and one or more synergistic metals; the metal-organic framework ligand contains lone pairs of electrons and electron-withdrawing groups, which can strongly coordinate with the active component metal ions; the support is one or more of coconut shell charcoal, wood charcoal, and coal-based charcoal. Preferably, the copper salt is copper chloride, copper nitrate, or copper sulfate.

[0008] Preferably, the copper ions in the copper salt are loaded in the catalyst at an amount of 0.5-8 wt%.

[0009] Preferably, the synergistic metal is lithium, strontium, potassium, cobalt, nickel, chromium, cesium, ruthenium, or gold.

[0010] Preferably, the synergistic metal is loaded in the catalyst at an amount of 0.05-5 wt%.

[0011] Preferably, the metal-organic framework ligand is two or more selected from 2-methylimidazolium, 1,2-dimethylimidazolium, 2-nitroimidazolium, benzimidazole, 2,2'-biimidazole, 1,3,5-tris(4-pyrazolyl)benzene, 1,3-dimethyl-2-imidazolinone, imidazol-4-carboxylic acid, benzotriazole, terephthalic acid, disodium terephthalate, 2,5-dihydroxyterephthalic acid, sodium isophthalate-5-sulfonate, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium hydrogen sulfate, tetrapropylammonium chloride, tetrapropylammonium bromide, triphenylamine, ammonium citrate, 2,2'-bipyridine, or biphenylcarboxylic acid.

[0012] Preferably, the mass fraction of the metal-organic framework ligand in the catalyst is 1-10 wt%.

[0013] Preferably, the carrier is coconut shell charcoal as the catalyst carrier.

[0014] Preferably, the specific surface area of ​​the carrier is 500–1500 m². 2 / g, density is 300~1000 kg / m³ 3 .

[0015] On the other hand, the present invention provides a method for preparing a composite metal-organic framework catalyst for the acetylene hydrochlorination reaction as described in the first aspect of the present invention, comprising the following steps: Copper salt, synergistic metal salt, and metal-organic framework ligand were dissolved sequentially in a solvent and stirred until a homogeneous solution was formed. A support was added, the solution was impregnated in a water bath, and then dried in a forced-air oven to obtain a composite metal-organic framework catalyst.

[0016] Preferably, the solvent is one or more of water, anhydrous ethanol, isopropanol, N-methylpyrrolidone, N,N-dimethylformamide, acetone, ethylenediamine, acetonitrile, or hydrochloric acid.

[0017] Preferably, the stirring time is 3-6 hours.

[0018] Preferably, the water bath temperature is 60-90 degrees Celsius.

[0019] Preferably, the soaking time is 4-15 h and the drying temperature is 90-120 degrees Celsius.

[0020] Finally, the present invention provides the application of the composite metal-organic framework catalyst described in the first or second aspect of the present invention in the acetylene hydrochlorination reaction.

[0021] The beneficial effects of this invention are as follows: (1) The ligand required for the composite metal-organic framework catalyst synthesized in this invention contains multiple metal coordination sites. With metal ions as the center, the ligands coordinate with each other through self-assembly to form a three-dimensional interconnected porous network structure. It has a strong anchoring and dispersing effect on metal ions. While improving the active sites of the catalyst, it greatly inhibits the reduction of high-valence metals and the aggregation between metal ions, improves the adsorption of reactants and the anti-carbon deposition performance, thereby improving the activity and long-term stability of the catalyst.

[0022] (2) The composite metal-organic framework catalyst prepared by the present invention is well compatible with the current chlor-alkali plant process and can be used directly without modifying the existing industrial tubular fixed bed reactor.

[0023] (3) The composite metal-organic framework catalyst prepared by the present invention is used for the acetylene hydrochlorination reaction. It has the advantages of high activity and stability, good selectivity of target products, strong resistance to carbon deposition, low cost, good performance, and simple and safe preparation process. Its industrial application prospects are huge. Attached Figure Description

[0024] Figure 1 The graph shows the change in acetylene conversion rate (%) with reaction time (h) as shown in Examples 5, 5, and 8. Detailed Implementation

[0025] The preferred embodiments of the present invention will be further described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0026] The following lists the common reaction conditions for Examples 1-10 and Comparative Examples 1-8: reaction temperature 180°C, reaction pressure atmospheric pressure, and acetylene volume hourly space velocity (VHSV) of 180 h⁻¹. -1 The loading of the composite metal-organic framework catalyst was 1.5 g, and the volumetric flow rate ratio of hydrogen chloride to acetylene gas was 1.1:1.

[0027] Example 1 Copper chloride and the synergistic metal salt nickel chloride were weighed and dissolved in 9 g of ethanol aqueous solution. Then, 1,2-dimethylimidazole and disodium terephthalate metal-organic framework ligands were added sequentially and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then immersed in a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, the synergistic nickel loading was 2 wt%, the ethanol content in the solution was 45% by mass, and the mass fractions of 1,2-dimethylimidazole and disodium terephthalate metal-organic framework ligands in the catalyst were 3% and 2%, respectively. The catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction were recorded in Table 1.

[0028] Example 2 Copper chloride and the synergistic metal salt nickel chloride were weighed and dissolved in 9 g of ethanol aqueous solution. Then, benzimidazole and disodium terephthalate metal-organic framework ligands were added sequentially and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then immersed in a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, the synergistic nickel loading was 2 wt%, the ethanol content in the solution was 45% by mass, and the mass fractions of benzimidazole and disodium terephthalate in the catalyst were 2.5% and 2%, respectively. The catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction are recorded in Table 1.

[0029] Example 3 Copper chloride and the synergistic metal salt nickel chloride were weighed and dissolved in 9 g of ethanol aqueous solution. Then, 2-methylimidazole and sodium isophthalic acid-5-sulfonate metal-organic framework ligands were added sequentially and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then immersed in a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, the synergistic nickel loading was 2 wt%, the ethanol content in the solution was 45% by mass, and the mass fractions of 2-methylimidazole and sodium isophthalic acid-5-sulfonate in the catalyst were 3% and 2%, respectively. The catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction were recorded in Table 1.

[0030] Example 4 Copper chloride and the synergistic metal salt nickel chloride were dissolved in 9 g of DMF aqueous solution. Imidazole-4-carboxylic acid and disodium terephthalate metal-organic framework ligands were then added sequentially and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then immersed in a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, the synergistic nickel loading was 2 wt%, the DMF content in the solution was 45% by mass, and the mass fractions of imidazole-4-carboxylic acid and disodium terephthalate in the catalyst were 3.2% and 2%, respectively. Catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction are recorded in Table 1.

[0031] Example 5 Copper chloride and the synergistic metal salt nickel chloride were weighed and dissolved in 9 g of acetonitrile aqueous solution. Then, 2,2'-biimidazole and disodium terephthalate metal-organic framework ligands were added sequentially and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then immersed in a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, the synergistic nickel loading was 2 wt%, the acetonitrile content in the solution was 45% by mass, and the mass fractions of 2,2'-biimidazole and disodium terephthalate in the catalyst were 3% and 2%, respectively. The catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction were recorded in Table 1.

[0032] Example 6 Copper chloride and the synergistic metal salt cobalt chloride were dissolved in 9 g of acetonitrile aqueous solution. Then, 2,2'-biimidazole and disodium terephthalate metal-organic framework ligands were added sequentially and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then immersed in a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, the synergistic cobalt loading was 2 wt%, the acetonitrile content in the solution was 45% by mass, and the mass fractions of 2,2'-biimidazole and disodium terephthalate in the catalyst were 3% and 2%, respectively. Catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction are recorded in Table 1.

[0033] Example 7 Copper chloride and the synergistic metal salt nickel chloride were weighed and dissolved in 9 g of ethylenediamine aqueous solution. Then, 2-nitroimidazole and disodium terephthalate metal-organic framework ligands were added sequentially and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then immersed in a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, the synergistic nickel loading was 2 wt%, the ethylenediamine content in the solution was 45% by mass, and the mass fractions of 2-nitroimidazole and disodium terephthalate in the catalyst were 3.5% and 2%, respectively. The catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction were recorded in Table 1.

[0034] Example 8 Copper chloride and the synergistic metal salt nickel chloride were weighed and dissolved in 9 g of N-methylpyrrolidone aqueous solution. Then, 1,2-dimethylimidazole and biphenyl dicarboxylic acid metal-organic framework ligands were added sequentially and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then immersed in a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, the synergistic nickel loading was 2 wt%, N-methylpyrrolidone accounted for 40% of the solution by mass, and the mass fractions of 1,2-dimethylimidazole and biphenyl dicarboxylic acid in the catalyst were 4% and 3%, respectively. The catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction were recorded in Table 1.

[0035] Example 9 Copper chloride and the synergistic metal salt nickel chloride were dissolved in 9 g of acetonitrile aqueous solution. Then, benzotriazole and 1,2,4,5-benzenetetracarboxylic acid (BMA) metal-organic framework ligands were added sequentially and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then immersed in a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, the synergistic nickel loading was 2 wt%, the acetonitrile content in the solution was 50% by mass, and the mass fractions of benzotriazole and 1,2,4,5-benzenetetracarboxylic acid in the catalyst were 3.5% and 2%, respectively. The catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction are recorded in Table 1.

[0036] Example 10 Copper chloride and the synergistic metal salt nickel chloride were weighed and dissolved in 9 g of acetonitrile aqueous solution. Imidazole-4-carboxylic acid and 2,5-dihydroxyterephthalic acid (2,5-dihydroxyterephthalic acid) metal-organic framework ligands were then added sequentially and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then immersed in a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, the synergistic nickel loading was 2 wt%, the acetonitrile content in the solution was 45% by mass, and the mass fractions of imidazole-4-carboxylic acid and 2,5-dihydroxyterephthalic acid in the catalyst were 3% and 2%, respectively. The catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction are recorded in Table 1.

[0037] Comparative Example 1 Copper chloride and synergistic lithium chloride were weighed and dissolved in 9 g of deionized water, and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then transferred to a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, and the synergistic lithium loading was 2 wt%. Catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction were recorded in Table 2.

[0038] Comparative Example 2 Copper chloride and synergistic metal salt strontium chloride were weighed and dissolved in 9 g of deionized water, and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then transferred to a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, and the synergistic strontium loading was 2 wt%. Catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction were recorded in Table 2.

[0039] Comparative Example 3 Copper chloride and potassium chloride (a synergistic metal salt) were weighed and dissolved in 9 g of deionized water, and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then transferred to a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, and the synergistic potassium loading was 2 wt%. Catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction were recorded in Table 2.

[0040] Comparative Example 4 Copper chloride and cobalt chloride (a synergistic metal salt) were weighed and dissolved in 9 g of deionized water, and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then transferred to a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, and the cobalt loading was 2 wt%. Catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction were recorded in Table 2.

[0041] Comparative Example 5 Copper chloride and synergistic nickel chloride were weighed and dissolved in 9 g of deionized water, and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then transferred to a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, and the synergistic nickel loading was 2 wt%. Catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction were recorded in Table 2.

[0042] Comparative Example 6 Copper chloride and synergistic metal salt chromium chloride were weighed and dissolved in 9 g of deionized water, and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min, then transferred to a 60℃ constant temperature water bath for 6 h, and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5 wt%, and the synergistic metal cobalt loading was 2 wt%. Catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction were recorded in Table 2.

[0043] Comparative Example 7 Copper chloride and cesium chloride (a synergistic metal salt) were weighed and dissolved in 9 g of deionized water, and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60°C for 30 min. It was then transferred to a 60°C constant temperature water bath for 6 h and dried in a 120°C forced-air drying oven for 4 h. The copper loading was 5 wt%, and the synergistic cesium loading was 2 wt%. Catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction were recorded in Table 2.

[0044] Comparative Example 8 Copper chloride was weighed and dissolved in 9 g of deionized water, and stirred until completely dissolved. 5 g of coconut shell carbon support was added to the solution, and the mixture was sonicated at 60℃ for 30 min. It was then transferred to a 60℃ constant temperature water bath for 6 h and dried in a 120℃ forced-air drying oven for 4 h. The copper loading was 5%. Catalyst performance was evaluated under the above reaction conditions, and the initial conversion rate and the decrease in conversion rate after 10 hours of reaction were recorded in Table 2.

[0045] Table 1. Comparison of the performance of auxiliary metals and ligands in the catalytic hydrochlorination of acetylene by copper-based catalysts.

[0046] Table 2 Comparison of the performance of auxiliary metals in the catalytic hydrochlorination of acetylene by copper-based catalysts

[0047] To further investigate the activity and stability of the composite metal-organic framework catalyst of the present invention, the catalysts prepared in Example 5, Comparative Example 5, and Comparative Example 8 were selected respectively, and under the same reaction conditions: the volume hourly space velocity of acetylene gas was 60 h⁻¹. -1 The reaction temperature was 230℃, V(HCl):V(C2H2) = 1.1:1, and the catalyst loading was 4.5 g. Long-term stability experiments were conducted, with continuous reaction for 340 hours. The catalyst conversion rate as a function of reaction time is shown in the figure. Figure 1 .

[0048] From Table 1, Table 2 and Figure 1 It can be seen that the addition of metal promoters and metal-organic framework coordinators can improve the activity and stability of copper-based composite metal-organic framework catalysts to a certain extent, and can operate stably for a long period of time at higher temperatures, showing great potential for industrial application.

[0049] In this invention, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0050] Although the above embodiments have been shown and described, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Any changes, modifications, substitutions and variations made to the above embodiments by those skilled in the art are within the protection scope of the present invention.

Claims

1. A composite metal-organic framework catalyst for catalyzing the hydrochlorination reaction of acetylene, characterized in that, It includes an active component, a support, and a metal-organic framework ligand; the active component includes an active component copper salt and one or more synergistic metals; the support is one or more of coconut shell charcoal, wood charcoal, or coal charcoal; the metal-organic framework ligand contains lone pairs of electrons and electron-withdrawing groups, which can undergo strong coordination with the active component metal ions.

2. The composite metal-organic framework catalyst according to claim 1, characterized in that, The copper salt is CuCl2.

3. The composite metal-organic framework catalyst according to claim 1, characterized in that, The synergistic metal is lithium, strontium, potassium, cobalt, nickel, chromium, cesium, ruthenium, or gold.

4. The composite metal-organic framework catalyst according to claim 1, characterized in that, The metal-organic framework ligand is two or more of the following: 2-methylimidazolium, 1,2-dimethylimidazolium, 2-nitroimidazolium, benzimidazole, 2,2'-biimidazole, 1,3,5-tris(4-pyrazolyl)benzene, 1,3-dimethyl-2-imidazolinone, imidazol-4-carboxylic acid, benzotriazole, terephthalic acid, disodium terephthalate, 2,5-dihydroxyterephthalic acid, sodium isophthalate-5-sulfonate, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium hydrogen sulfate, tetrapropylammonium chloride, tetrapropylammonium bromide, triphenylamine, ammonium citrate, 2,2'-bipyridine, or biphenylcarboxylic acid.

5. The composite metal-organic framework catalyst according to claim 1, characterized in that, The copper salt contains 0.5–8 wt% copper ions in the catalyst, the cooperating metal contains 0.05–5 wt% cooperating metal in the catalyst, and the support has a specific surface area of ​​500–1500 m². 2 / g, density is 300~1000 kg / m³ 3 .

6. The composite metal-organic framework catalyst according to claim 1, characterized in that, The mass fraction of the metal-organic framework ligand in the catalyst is 1–10 wt%.

7. A method for preparing a composite metal-organic framework catalyst according to any one of claims 1-6, characterized in that, Copper salt, synergistic metal salt, and metal-organic framework ligand were dissolved sequentially in a solvent and stirred until a homogeneous solution was formed. A support was then added, the solution was impregnated in a water bath, and dried in an oven to obtain a composite metal-organic framework catalyst.

8. The method for preparing the composite metal-organic framework catalyst according to claim 7, characterized in that, The solvent is one or more of water, anhydrous ethanol, isopropanol, N-methylpyrrolidone, N,N-dimethylformamide, acetone, ethylenediamine, acetonitrile, or hydrochloric acid.

9. The method for preparing the composite metal-organic framework catalyst according to claim 7, characterized in that, The water bath temperature is 60-90 degrees Celsius, the soaking time is 4-15 hours, and the drying temperature is 90-120 degrees Celsius.

10. The application of a composite metal-organic framework catalyst according to any one of claims 1-6 in the catalytic hydrochlorination reaction of acetylene.

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