An acetylene dimerization functionalized ionic liquid phase catalyst, its preparation method and application

Abstract

The application discloses an ethyne dimerization functional ionic liquid phase catalyst and a preparation method and application thereof. The ethyne dimerization functional ionic liquid phase catalyst is composed of an active component and a functional acidic ionic liquid; the active component is one of cuprous chloride, copper phthalocyanine and copper phosphate; the functional acidic ionic liquid is at least one selected from ionic liquids shown in formula (I)-(IV) and at least includes one ionic liquid A selected from ionic liquids shown in formula (I) or (II), and the total mass percentage of the ionic liquid A in the total mass of the functional acidic ionic liquid is at least 58%. The catalyst has the characteristics of simple composition, easy preparation process, green environmental protection, high ethyne single-pass conversion rate and good ethynylacetylene selectivity.

Description

Technical Field

[0001] This invention relates to an acetylene dimerization catalyst, its preparation method, and its application in the synthesis of vinylacetylene. Background Technology

[0002] With the continuous maturation of coal-to-low-carbon alkyne (C2-C4) technology, alkyne chemical technology using low-carbon alkynes as raw materials will become an important development direction in the post-petrochemical era. Acetylene, as the "mother of organic synthesis industry," has a wide range of applications. Among them, vinyl acetylene, as a downstream product of acetylene, is an important fine chemical intermediate and a major raw material for the production of chloroprene monomer chloroprene rubber. It can also be used in the production of 4-chlorophthalic anhydride, adiponitrile, butadiene, dimethyl ethyl ketone, benzene, styrene, and many traditional petrochemical products, thereby effectively alleviating the current industrial production's dependence on the petrochemical industry. Therefore, the domestic acetylene method has a strong advantage and is the main method for producing chloroprene. However, the acetylene method still has many problems, such as: (1) complex catalyst composition; (2) low single-pass conversion rate of acetylene; (3) low selectivity of vinyl acetylene; (4) many by-products in the reaction process, which greatly reduce the selectivity of vinyl acetylene and reduce the service life of the catalyst.

[0003] Currently, the production of vinylacetylene primarily involves catalytic dimerization of acetylene. The acetylene conversion rate and vinylacetylene selectivity of the catalyst are crucial. The production of vinylacetylene through acetylene dimerization mainly employs aqueous Nieuwland catalysts and non-aqueous Nieuwland catalysts. The main drawback of aqueous Nieuwland catalysts is the low solubility of acetylene in the catalytic reaction system during use. While non-aqueous catalysts can improve acetylene solubility to some extent, they still cannot meet the requirements for highly efficient and selective synthesis of vinylacetylene. Furthermore, both aqueous and non-aqueous Nieuwland catalytic systems suffer from drawbacks such as complex catalyst composition (including active components, solvents, co-solvents, ligands, and additives), cumbersome preparation, stringent storage and usage conditions, and difficulties in catalyst recovery.

[0004] Therefore, current acetylene dimerization catalysts still need improvement.

[0005] Ionic liquids are organic salts that are liquid at room temperature, composed of organic cations and inorganic or organic anions; they are commonly referred to as room-temperature ionic liquids. As a novel type of polar solvent, ionic liquids have virtually no vapor pressure, are non-flammable, non-volatile, and possess excellent chemical and thermal stability. They are recyclable and environmentally friendly, hence the term "green" chemical solvent, and can be used to replace traditional volatile and toxic solvents. Furthermore, the high polarity, hydrophobicity, and solubility of ionic liquids can be altered by selecting different cations, anions, and side-chain substituents, thus they are also called "designed solvents." Ionic liquids are considered one of the most promising green solvents and catalysts of the 21st century and have been applied in many fields such as biocatalysis, separation science, and electrochemistry. Our previous work also revealed that ionic liquids can selectively adsorb reactant gases and products. For different reaction atmospheres, ionic liquids can be functionally modified (modified / functionalized) to enrich reactant gases while repelling products. Currently, there are no application cases of modified / functionalized ionic liquid catalysts in the dimerization of acetylene to vinylacetylene. Therefore, based on the characteristics of the acetylene dimerization reaction process, functionalized ionic liquids can be introduced to further optimize and apply this reaction. Summary of the Invention

[0006] This invention aims to solve the problems of complex composition and low single-pass acetylene conversion rate in existing acetylene dimerization catalytic systems, and provides a simple and green acetylene dimerization functionalized ionic liquid phase catalyst, its preparation, and its application in the synthesis of vinylacetylene.

[0007] In a first aspect, the present invention provides an acetylene dimerization functionalized ionic liquid phase catalyst, which is composed of an active component and a functionalized acidic ionic liquid; wherein the mass ratio of the active component to the functionalized acidic ionic liquid in the catalyst is 2.5-20:100.

[0008] The active component is one of cuprous chloride (CuCl), copper phthalocyanine (CuPc), and copper phosphate (Cu3(PO4)2);

[0009] The functionalized acidic ionic liquid is selected from at least one of the ionic liquids shown in formulas (I), (II), (III) and (IV), and includes at least one ionic liquid A, wherein the ionic liquid A is selected from the ionic liquid shown in formula (I) or (II), and the total mass of the ionic liquid A accounts for at least 58% of the total mass of the functionalized acidic ionic liquid.

[0010]

[0011] In formula (I), n1 represents a natural number between 1 and 4; Y1 represents a carboxyl group or a sulfonic acid group; X1 - Represents Cl- BF4 - or HSO4 - ;

[0012] In formula (II), R1 is H or a C1-C2 alkyl group; n3 represents a natural number between 1 and 4; Y3 represents a carboxyl group or a sulfonic acid group; X3 - Represents Cl - BF4 - or HSO4 - ;

[0013] In equation (III), n2 represents a natural number between 1 and 4; Y2 represents H; X2 - Represents Cl - BF4 - or HSO4 - ;

[0014] In formula (IV), R2 is H or a C1-C2 alkyl group; n4 represents a natural number between 1 and 4; Y4 represents H; X4 - Represents Cl - BF4 - or HSO4 - .

[0015] Preferably, the functionalized acidic ionic liquid is selected from one of the following: 1-butylsulfonic acid-3-methylimidazolium hydrogen sulfate, 1-ethylcarboxylic acid-3-methylimidazolium chloride, N-carboxymethylpyridine chloride, N-sulfonic acid ethylpyridine tetrafluoroborate, N-sulfonic acid butylpyridine hydrogen sulfate, 1-ethylsulfonic acid-3-methylimidazolium chloride, N-sulfonic acid ethylpyridine hydrogen sulfate, 1-methanesulfonic acid-3-methylimidazolium chloride, a combination of N-carboxymethylpyridine chloride and 1-ethylsulfonic acid-3-methylimidazolium chloride, a combination of N-sulfonic acid ethylpyridine hydrogen sulfate and 1,3-dimethylimidazolium tetrafluoroborate, and a combination of N-ethylpyridine hydrogen sulfate and 1-methanesulfonic acid-3-methylimidazolium chloride.

[0016] Secondly, the present invention provides a method for preparing an acetylene dimerization functionalized acidic ionic liquid phase catalyst, comprising the following steps:

[0017] (1) Add acetylene dimerized functionalized acidic ionic liquid to a bubbling reactor. Under the temperature conditions of 50-300℃, nitrogen gas is introduced at a flow rate of 5-20 ml / min for bubbling and stirring. Stirring is carried out to replace the impurity gas in the bubbling reactor and the functionalized acidic ionic liquid, so that the ionic liquid is fully melted and the viscosity is reduced.

[0018] (2) Maintain the heating temperature and nitrogen bubbling flow rate of step (1), add the active component in proportion through the sample inlet of the bubbling reactor, and continue stirring to fully mix the active component and the functionalized acidic ionic liquid to obtain the acetylene dimerization functionalized ionic liquid phase catalyst.

[0019] Thirdly, the present invention provides the application of the acetylene dimerization functionalized acidic ionic liquid phase catalyst in the synthesis of vinylacetylene.

[0020] Furthermore, the specific application involves adjusting the temperature of a bubbling reactor containing an acetylene dimerization functionalized ionic liquid phase catalyst to the target reaction temperature, and then introducing acetylene gas to carry out an acetylene dimerization reaction to generate vinylacetylene.

[0021] Furthermore, the reaction temperature is 50-135℃, preferably 80℃; the acetylene space velocity is 50-500 h⁻¹. -1 240h ​​preferred -1 .

[0022] Compared with the prior art, the present invention has at least the following beneficial effects:

[0023] (1) The catalyst of the present invention contains only active components and functionalized acidic ionic liquids, and has the characteristics of simple catalytic system components, easy preparation process, and green environmental protection.

[0024] (2) The catalyst of the present invention has the characteristics of high single-pass conversion rate of acetylene, good selectivity of vinyl acetylene and few by-products.

[0025] (3) The present invention employs functionalized ionic liquid phase catalysis technology, and designs functionalized ionic liquids for actual reaction conditions, which greatly improves the stability of copper active centers. At the same time, functionalized ionic liquids can selectively enrich acetylene and repel vinylacetylene, thereby improving the catalytic activity of the catalyst. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the catalyst evaluation process. Detailed Implementation

[0027] The technical solution of the present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto:

[0028] In the embodiments of this invention, the preparation of the catalyst and the acetylene dimerization reaction are carried out in... Figure 1 The procedure is carried out within the apparatus shown.

[0029] Unless otherwise specified in the embodiments of this invention, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained through conventional technical means or commercially available.

[0030] Example 1

[0031] (1) Add 200g of 1-butylsulfonic acid-3-methylimidazolium hydrogen sulfate ionic liquid to the bubbling reactor, introduce nitrogen gas at a flow rate of 5ml / min, raise the temperature of the bubbling reactor to 150℃, stir for 30min, so that the ionic liquid and impurity gas in the bubbling reactor are fully replaced.

[0032] (2) Maintain the temperature and nitrogen flow rate of the bubbling reactor in step (1), and add 25g CuCl into the reactor through the bubbling reactor inlet. The CuCl is weighed in a nitrogen-filled glove box, then transferred into the injector, and finally added through the inlet to avoid oxidation; then continue stirring for 1h to ensure that the CuCl and ionic liquid are fully mixed and homogeneous to obtain the CuCl-ionic liquid catalyst;

[0033] (3) Raise the temperature of the bubbling reactor to 80°C, switch the gas to acetylene, and maintain the acetylene space velocity at 240 h⁻¹. -1 The reaction proceeds to the dimerization of acetylene to form vinylacetylene.

[0034] (4) After the reaction begins, the tail gas is introduced into a gas chromatograph. A GDX-301 packed column is used to detect the conversion rate of acetylene and the selectivity of vinylacetylene in the tail gas. The performance data after stabilization are shown in Table 1.

[0035] Example 2

[0036] (1) Add 200g of 1-ethylcarboxylic acid-3-methylimidazolium chloride ionic liquid to a bubbling reactor, introduce nitrogen gas at a flow rate of 15ml / min, raise the temperature of the bubbling reactor to 120℃, stir for 30min, so that the ionic liquid and impurity gas in the bubbling reactor are fully replaced.

[0037] (2) Maintain the temperature and nitrogen flow rate of the bubbling reactor in step (1), and add 7.5g CuPc into the reactor through the bubbling reactor inlet. The CuPc is weighed in a nitrogen-filled glove box, then transferred into the injector, and finally added through the inlet to avoid oxidation; then continue stirring for 1h to ensure that the CuPc and ionic liquid are fully mixed and homogeneous to obtain the CuPc-ionic liquid catalyst;

[0038] (3) Raise the temperature of the bubbling reactor to 80°C, switch the gas to acetylene, and maintain the acetylene space velocity at 240 h⁻¹. -1 The reaction proceeds to the dimerization of acetylene to form vinylacetylene.

[0039] (4) After the reaction begins, the tail gas is introduced into a gas chromatograph. A GDX-301 packed column is used to detect the conversion rate of acetylene and the selectivity of vinylacetylene in the tail gas. The performance data after stabilization are shown in Table 1.

[0040] Example 3

[0041] (1) Add 200g of N-carboxymethylpyridine chloride ionic liquid to the bubbling reactor, introduce nitrogen gas at a flow rate of 15ml / min, raise the temperature of the bubbling reactor to 200℃, stir for 30min, so that the ionic liquid and impurity gas in the bubbling reactor are fully replaced.

[0042] (2) Maintain the temperature and nitrogen flow rate of the bubbling reactor in step (1), and add 11.5g CuCl into the reactor through the bubbling reactor inlet. The CuCl is weighed in a nitrogen-filled glove box, then transferred into the injector, and finally added through the inlet to avoid oxidation; then continue stirring for 1h to ensure that the CuCl and ionic liquid are fully mixed and homogeneous to obtain the CuCl-ionic liquid catalyst;

[0043] (3) Raise the temperature of the bubbling reactor to 80°C, switch the gas to acetylene, and maintain the acetylene space velocity at 240 h⁻¹. -1 The reaction proceeds to the dimerization of acetylene to form vinylacetylene.

[0044] (4) After the reaction begins, the tail gas is introduced into a gas chromatograph. A GDX-301 packed column is used to detect the conversion rate of acetylene and the selectivity of vinylacetylene in the tail gas. The performance data after stabilization are shown in Table 1.

[0045] Example 4

[0046] (1) Add 200g of N-sulfonic acid ethylpyridine tetrafluoroborate ionic liquid to the bubbling reactor, introduce nitrogen gas at a flow rate of 10ml / min, raise the temperature of the bubbling reactor to 60℃, stir for 30min, so that the ionic liquid and impurity gas in the bubbling reactor are fully replaced.

[0047] (2) Maintain the temperature and nitrogen flow rate of the bubbling reactor in step (1), and add 21g of Cu3(PO4)2 into the reactor through the bubbling reactor inlet. The Cu3(PO4)2 was weighed in a nitrogen-filled glove box, then transferred into the injector, and finally added through the inlet to avoid oxidation; then continue stirring for 1h to ensure that the Cu3(PO4)2 and the ionic liquid are fully mixed and homogeneous to obtain the Cu3(PO4)2-ionic liquid catalyst;

[0048] (3) Raise the temperature of the bubbling reactor to 80°C, switch the gas to acetylene, and maintain the acetylene space velocity at 240 h⁻¹. -1 The reaction proceeds to the dimerization of acetylene to form vinylacetylene.

[0049] (4) After the reaction begins, the tail gas is introduced into a gas chromatograph. A GDX-301 packed column is used to detect the conversion rate of acetylene and the selectivity of vinylacetylene in the tail gas. The performance data after stabilization are shown in Table 1.

[0050] Example 5

[0051] (1) Add 200g of N-sulfonic acid butylpyridine hydrogen sulfate ionic liquid to the bubbling reactor, introduce nitrogen gas at a flow rate of 10ml / min, raise the temperature of the bubbling reactor to 90℃, stir for 30min, so that the ionic liquid and impurity gas in the bubbling reactor are fully replaced.

[0052] (2) Maintain the temperature and nitrogen flow rate of the bubbling reactor in step (1), and add 5g of CuPc into the reactor through the bubbling reactor inlet. The CuPc is weighed in a nitrogen-filled glove box, then transferred into the injector, and finally added through the inlet to avoid oxidation; then continue stirring for 1h to ensure that the CuPc and ionic liquid are fully mixed and homogeneous to obtain the CuPc-ionic liquid catalyst;

[0053] (3) Raise the temperature of the bubbling reactor to 80°C, switch the gas to acetylene, and maintain the acetylene space velocity at 240 h⁻¹. -1 The reaction proceeds to the dimerization of acetylene to form vinylacetylene.

[0054] (4) After the reaction begins, the tail gas is introduced into a gas chromatograph. A GDX-301 packed column is used to detect the conversion rate of acetylene and the selectivity of vinylacetylene in the tail gas. The performance data after stabilization are shown in Table 1.

[0055] Example 6

[0056] (1) Add 80g of N-carboxymethylpyridine chloride ionic liquid and 110g of 1-ethylsulfonic acid-3-methylimidazolium chloride ionic liquid to a bubbling reactor, introduce nitrogen gas at a flow rate of 15ml / min, raise the temperature of the bubbling reactor to 50℃, stir for 30min, so that the ionic liquid and impurity gas in the bubbling reactor are fully replaced.

[0057] (2) Maintain the temperature and nitrogen flow rate of the bubbling reactor in step (1), and add 22g CuCl into the reactor through the bubbling reactor inlet. The CuCl is weighed in a nitrogen-filled glove box, then transferred into the injector, and finally added through the inlet to avoid introducing impurities; then continue stirring for 1h to ensure that the CuCl and ionic liquid are fully mixed and homogeneous to obtain the CuCl-ionic liquid catalyst;

[0058] (3) Raise the temperature of the bubbling reactor to 80°C, switch the gas to acetylene, and maintain the acetylene space velocity at 240 h⁻¹. -1 The reaction proceeds to the dimerization of acetylene to form vinylacetylene.

[0059] (4) After the reaction begins, the tail gas is introduced into a gas chromatograph. A GDX-301 packed column is used to detect the conversion rate of acetylene and the selectivity of vinylacetylene in the tail gas. The performance data after stabilization are shown in Table 1.

[0060] Example 7

[0061] (1) Add 128g of N-sulfonic acid ethylpyridine hydrogen sulfate ionic liquid and 80g of 1,3-dimethylimidazolium tetrafluoroborate ionic liquid to a bubbling reactor, introduce nitrogen gas at a flow rate of 5ml / min, raise the temperature of the bubbling reactor to 140℃, stir for 30min, so that the ionic liquid and impurity gas in the bubbling reactor are fully replaced.

[0062] (2) Maintain the temperature and nitrogen flow rate of the bubbling reactor in step (1), and add 15g of Cu3(PO4)2 into the reactor through the bubbling reactor inlet. The Cu3(PO4)2 is weighed in a nitrogen-filled glove box, then transferred into the injector, and finally added through the inlet to avoid introducing impurities; then continue stirring for 1h to ensure that the Cu3(PO4)2 and the ionic liquid are fully mixed and homogeneous to obtain the Cu3(PO4)2-ionic liquid catalyst;

[0063] (3) Adjust the temperature of the bubbling reactor to 80℃, switch the gas to acetylene, and maintain the acetylene space velocity at 240 h⁻¹. -1 The reaction proceeds to the dimerization of acetylene to form vinylacetylene.

[0064] (4) After the reaction begins, the tail gas is introduced into a gas chromatograph. A GDX-301 packed column is used to detect the conversion rate of acetylene and the selectivity of vinylacetylene in the tail gas. The performance data after stabilization are shown in Table 1.

[0065] Example 8

[0066] (1) Add 80g of N-ethylpyridine hydrogen sulfate ionic liquid and 125g of 1-methanesulfonic acid-3-methylimidazolium chloride ionic liquid to a bubbling reactor, introduce nitrogen gas at a flow rate of 15ml / min, raise the temperature of the bubbling reactor to 140℃, stir for 30min, so that the ionic liquid and impurity gas in the bubbling reactor are fully replaced.

[0067] (2) Maintain the temperature and nitrogen flow rate of the bubbling reactor in step (1), and add 12.5g CuPc into the reactor through the bubbling reactor inlet. The CuPc is weighed in a nitrogen-filled glove box, then transferred into the injector, and finally added through the inlet to avoid introducing impurities; then continue stirring for 1h to ensure that the CuPc and ionic liquid are fully mixed and homogeneous to obtain the CuPc-ionic liquid catalyst;

[0068] (3) Adjust the temperature of the bubbling reactor to 80℃, switch the gas to acetylene, and maintain the acetylene space velocity at 240 h⁻¹.-1 The reaction proceeds to the dimerization of acetylene to form vinylacetylene.

[0069] (4) After the reaction begins, the tail gas is introduced into a gas chromatograph. A GDX-301 packed column is used to detect the conversion rate of acetylene and the selectivity of vinylacetylene in the tail gas. The performance data after stabilization are shown in Table 1.

[0070] Comparative Example 1

[0071] The catalyst was prepared according to the method in Example 1 of patent CN 103285931B, and the temperature of the bubbling reactor was adjusted to 80°C and the acetylene space velocity was maintained at 240 h⁻¹ according to the method in Example 1. -1 The reaction of acetylene dimerization to vinylacetylene was carried out, and the catalyst performance was tested according to the method of Example 1. The data are shown in Table 1.

[0072] Comparative Example 2

[0073] The catalyst was prepared according to the method in Example 13 of patent CN 103285925B, and the temperature of the bubbling reactor was adjusted to 80°C and the acetylene space velocity was maintained at 240 h⁻¹ according to the method in Example 1. -1 The reaction of acetylene dimerization to vinylacetylene was carried out, and the catalyst performance was tested according to the method of Example 1. The data are shown in Table 1.

[0074] Comparative Example 3

[0075] The catalyst was prepared according to the method in Example 3 of patent CN 103467236A, and the temperature of the bubbling reactor was adjusted to 80°C and the acetylene space velocity was maintained at 240 h⁻¹ according to the method in Example 1. -1 The reaction of acetylene dimerization to vinylacetylene was carried out, and the catalyst performance was tested according to the method of Example 1. The data are shown in Table 1.

[0076] Comparative Example 4

[0077] (1) Add 200g of 1-ethyl-3-methylimidazolium hydroxide alkaline ionic liquid to the bubbling reactor, introduce nitrogen gas at a flow rate of 10ml / min, raise the temperature of the bubbling reactor to 90℃, stir for 30min, so that the ionic liquid and impurity gas in the bubbling reactor are fully replaced.

[0078] (2) Maintain the temperature and nitrogen flow rate of the bubbling reactor in step (1), and add 15g of Cu3(PO4) into the reactor through the bubbling reactor inlet. The Cu3(PO4) was weighed in a nitrogen-filled glove box, then transferred into the injector, and finally added through the inlet to avoid oxidation; then continue stirring for 1h to ensure that the Cu3(PO4) and ionic liquid are fully mixed and homogeneous to obtain the Cu3(PO4)-ionic liquid catalyst;

[0079] (3) Raise the temperature of the bubbling reactor to 140℃, switch the gas to acetylene, and maintain the acetylene space velocity at 180 h⁻¹. -1 The reaction proceeds to the dimerization of acetylene to form vinylacetylene.

[0080] (4) After the reaction begins, the tail gas is introduced into a gas chromatograph. A GDX-301 packed column is used to detect the conversion rate of acetylene and the selectivity of vinylacetylene in the tail gas. The performance data after stabilization are shown in Table 1.

[0081] Comparative Example 5

[0082] (1) Add 200g of 1-butyl-3-methylimidazolium hydrogen sulfate ionic liquid to the bubbling reactor, introduce nitrogen gas at a flow rate of 10ml / min, raise the temperature of the bubbling reactor to 60℃, stir for 30min, so that the ionic liquid and impurity gas in the bubbling reactor are fully replaced.

[0083] (2) Maintain the temperature and nitrogen flow rate of the bubbling reactor in step (1), and add 25g CuCl into the reactor through the bubbling reactor inlet. The CuCl is weighed in a nitrogen-filled glove box, then transferred into the injector, and finally added through the inlet to avoid oxidation; then continue stirring for 1h to ensure that the CuCl and ionic liquid are fully mixed and homogeneous to obtain the CuCl-ionic liquid catalyst;

[0084] (3) Raise the temperature of the bubbling reactor to 80°C, switch the gas to acetylene, and maintain the acetylene space velocity at 240 h⁻¹. -1 The reaction proceeds to the dimerization of acetylene to form vinylacetylene.

[0085] (4) After the reaction begins, the tail gas is introduced into a gas chromatograph. A GDX-301 packed column is used to detect the conversion rate of acetylene and the selectivity of vinylacetylene in the tail gas. The performance data after stabilization are shown in Table 1.

[0086] Comparative Example 6

[0087] (1) Add 200g of 1-ethyl-3-methylimidazolium chloride ionic liquid to a bubbling reactor, introduce nitrogen gas at a flow rate of 15ml / min, raise the temperature of the bubbling reactor to 100℃, and stir for 30min to fully replace the ionic liquid and impurity gas in the bubbling reactor.

[0088] (2) Maintain the temperature and nitrogen flow rate of the bubbling reactor in step (1), and add 7.5g CuPc into the reactor through the bubbling reactor inlet. The CuPc is weighed in a nitrogen-filled glove box, then transferred into the injector, and finally added through the inlet to avoid oxidation; then continue stirring for 1h to ensure that the CuPc and ionic liquid are fully mixed and homogeneous to obtain the CuPc-ionic liquid catalyst;

[0089] (3) Raise the temperature of the bubbling reactor to 80°C, switch the gas to acetylene, and maintain the acetylene space velocity at 240 h⁻¹. -1 The reaction proceeds to the dimerization of acetylene to form vinylacetylene.

[0090] (4) After the reaction begins, the tail gas is introduced into a gas chromatograph. A GDX-301 packed column is used to detect the conversion rate of acetylene and the selectivity of vinylacetylene in the tail gas. The performance data after stabilization are shown in Table 1.

[0091] Comparative Example 7

[0092] (1) Add 208g of 1,3-dimethylimidazolium tetrafluoroborate ionic liquid to a bubbling reactor, introduce nitrogen gas at a flow rate of 5ml / min, raise the temperature of the bubbling reactor to 140℃, stir for 30min, so that the ionic liquid and impurity gas in the bubbling reactor are fully replaced.

[0093] (2) Maintain the temperature and nitrogen flow rate of the bubbling reactor in step (1), and add 15g of Cu3(PO4)2 into the reactor through the bubbling reactor inlet. The Cu3(PO4)2 is weighed in a nitrogen-filled glove box, then transferred into the injector, and finally added through the inlet to avoid introducing impurities; then continue stirring for 1h to ensure that the Cu3(PO4)2 and the ionic liquid are fully mixed and homogeneous to obtain the Cu3(PO4)2-ionic liquid catalyst;

[0094] (3) Adjust the temperature of the bubbling reactor to 80℃, switch the gas to acetylene, and maintain the acetylene space velocity at 240 h⁻¹. -1 The reaction proceeds to the dimerization of acetylene to form vinylacetylene.

[0095] (4) After the reaction begins, the tail gas is introduced into a gas chromatograph. A GDX-301 packed column is used to detect the conversion rate of acetylene and the selectivity of vinylacetylene in the tail gas. The performance data after stabilization are shown in Table 1.

[0096] Comparative Example 8

[0097] (1) Add 205g of 1-methanesulfonic acid-3-methylimidazolium chloride ionic liquid to the bubbling reactor, introduce nitrogen gas at a flow rate of 15ml / min, raise the temperature of the bubbling reactor to 140℃, stir for 30min, so that the ionic liquid and impurity gas in the bubbling reactor are fully replaced.

[0098] (2) Maintain the temperature and nitrogen flow rate of the bubbling reactor in step (1), and add 12.5g CuPc into the reactor through the bubbling reactor inlet. The CuPc is weighed in a nitrogen-filled glove box, then transferred into the injector, and finally added through the inlet to avoid introducing impurities; then continue stirring for 1h to ensure that the CuPc and ionic liquid are fully mixed and homogeneous to obtain the CuPc-ionic liquid catalyst;

[0099] (3) Adjust the temperature of the bubbling reactor to 80℃, switch the gas to acetylene, and maintain the acetylene space velocity at 240 h⁻¹. -1 The reaction proceeds to the dimerization of acetylene to form vinylacetylene.

[0100] (4) After the reaction begins, the tail gas is introduced into a gas chromatograph. A GDX-301 packed column is used to detect the conversion rate of acetylene and the selectivity of vinylacetylene in the tail gas. The performance data after stabilization are shown in Table 1.

[0101] Table 1: Composition and Catalytic Performance Data of Ionic Liquid Catalysts in Examples and Comparative Examples

[0102]

[0103]

[0104] The formulas for calculating the acetylene conversion and vinylacetylene selectivity in the experimental data of acetylene dimerization to vinylacetylene listed in Table 1 are as follows:

[0105]

[0106]

[0107] The results of Comparative Examples 1-3 indicate that the acetylene dimerization reaction using catalysts reported in existing literature exhibits unsatisfactory acetylene conversion and product selectivity. The results of Comparative Example 4 show that when the catalyst is an alkaline ionic liquid, the conversion and selectivity of the acetylene dimerization reaction are also poor. The results of Comparative Example 5 and Example 1 show that when the catalyst lacks sulfonic acid groups, the conversion of the acetylene dimerization reaction decreases significantly, and the selectivity also decreases slightly.

[0108] Comparing Example 6 with Example 2, it can be seen that when the ionic liquid is changed from 1-ethyl-3-methylimidazolium chloride to 1-ethylcarboxylic acid-3-methylimidazolium chloride, the introduction of the carboxyl group can significantly improve the acetylene conversion rate.

[0109] Comparing Comparative Example 7 with Example 7, it can be seen that when the ionic liquid is selected as a combination of N-sulfonic acid ethylpyridine hydrogen sulfate and 1,3-dimethylimidazolium tetrafluoroborate, the acetylene conversion rate and product yield can be significantly improved compared with the use of 1,3-dimethylimidazolium tetrafluoroborate alone.

[0110] Comparing Comparative Example 8 with Example 8, it can be seen that when the ionic liquid uses a combination of N-ethylpyridine hydrogen sulfate and 1-methanesulfonic acid-3-methylimidazolium chloride, the acetylene conversion and product selectivity are slightly improved compared to using 1-methanesulfonic acid-3-methylimidazolium chloride alone.

Claims

1. The application of an acetylene dimerization functionalized ionic liquid phase catalyst in the synthesis of vinylacetylene, characterized in that: The acetylene dimerization functionalized ionic liquid phase catalyst is composed of an active component and a functionalized acidic ionic liquid; the mass ratio of the active component to the functionalized acidic ionic liquid in the catalyst is 2.5-20:

100. The active component is one of cuprous chloride, copper phthalocyanine, and copper phosphate. The functionalized acidic ionic liquid is selected from at least one of the ionic liquids shown in formulas (I), (II), (III), and (IV), and includes at least one ionic liquid A, wherein the ionic liquid A is selected from the ionic liquid shown in formula (I) or (II), and the total mass of the ionic liquid A accounts for at least 58% of the total mass of the functionalized acidic ionic liquid; （I） (II) (III) (IV) In formula (I), n1 represents a natural number between 1 and 4; Y1 represents a carboxyl group or a sulfonic acid group; X1 - Represents Cl - BF4 - or HSO4 - ; In formula (II), R1 is H or a C1-C2 alkyl group; n3 represents a natural number between 1 and 4; Y3 represents a carboxyl group or a sulfonic acid group; X3 - Represents Cl - BF4 - or HSO4 - ; In equation (III), n2 represents a natural number between 1 and 4; Y2 represents H; X2 - Represents Cl - BF4 - or HSO4 - ; In formula (IV), R2 is H or a C1-C2 alkyl group; n4 represents a natural number between 1 and 4; Y4 represents H; X4 - Represents Cl - BF4 - or HSO4 - .

2. The application as described in claim 1, characterized in that: The functionalized acidic ionic liquid is selected from one of the following: 1-butylsulfonic acid-3-methylimidazolium hydrogen sulfate, 1-ethylcarboxylic acid-3-methylimidazolium chloride, N-carboxymethylpyridine chloride, N-sulfonic acid ethylpyridine tetrafluoroborate, N-sulfonic acid butylpyridine hydrogen sulfate, 1-ethylsulfonic acid-3-methylimidazolium chloride, N-sulfonic acid ethylpyridine hydrogen sulfate, 1-methanesulfonic acid-3-methylimidazolium chloride, a combination of N-carboxymethylpyridine chloride and 1-ethylsulfonic acid-3-methylimidazolium chloride, a combination of N-sulfonic acid ethylpyridine hydrogen sulfate and 1,3-dimethylimidazolium tetrafluoroborate, and a combination of N-ethylpyridine hydrogen sulfate and 1-methanesulfonic acid-3-methylimidazolium chloride.

3. The application as described in claim 1, characterized in that: The preparation method of the acetylene dimerization functionalized ionic liquid phase catalyst is carried out according to the following steps: (1) Add the acetylene dimerized functionalized acidic ionic liquid to the bubbling reactor. Under the temperature conditions of 50-300℃, nitrogen gas is introduced at a flow rate of 5-20 ml / min for bubbling and stirring. Stir thoroughly to replace the impurity gas in the bubbling reactor and the functionalized acidic ionic liquid, so that the ionic liquid is fully melted and the viscosity is reduced. (2) Maintain the heating temperature and nitrogen bubbling flow rate of step (1), add the active component in proportion through the sample inlet of the bubbling reactor, and continue stirring to fully mix the active component and the functionalized acidic ionic liquid to obtain the acetylene dimerization functionalized ionic liquid phase catalyst.

4. The application as described in any one of claims 1-3, characterized in that: The specific application involves adjusting the temperature of a bubbling reactor containing an acetylene dimerization functionalized ionic liquid phase catalyst to the target reaction temperature, and then introducing acetylene gas to carry out an acetylene dimerization reaction to generate vinylacetylene.

5. The application as described in claim 4, characterized in that: The reaction temperature is 50-135℃; the acetylene space velocity is 50-500 h⁻¹. -1 .

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