Arylphosphine oxide ligand copper-based catalyst, preparation method thereof and application of aryl phosphine oxide ligand copper-based catalyst in acetylene hydrochlorination reaction
By using arylphosphine oxide ligand copper-based catalysts, the existing mercury-free catalysts have been solved, with low catalytic activity, poor selectivity and insufficient stability in the acetylene hydrochlorination reaction, and efficient preparation of vinyl chloride and long life of the catalyst are achieved.
Patent Information
- Application Number
- CN202510186532.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-20
- Publication Date
- 2025-05-27
AI Technical Summary
The mercury-free catalyst used in the existing acetylene hydrochlorination reaction has problems of low catalytic activity, poor selectivity and insufficient stability, especially in the presence of high impurities and reducing components.
An arylphosphine oxide ligand copper-based catalyst is used, which consists of activated carbon supported by arylphosphine oxide ligand, divalent copper salt, noble metal or indium-containing compounds. The catalytic performance is improved through synergistic catalytic action, and the excessive reduction of precious metals is prevented through metal coordination bonds and anchoring of activated carbon.
It has achieved high acetylene conversion and high vinyl chloride selectivity, and has good catalyst stability and is not easy to deactivate. It is suitable for low reaction temperature conditions and still shows good catalytic performance.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of vinyl chloride catalytic synthesis, and in particular to an aryl phosphine oxide ligand copper-based catalyst, a preparation method thereof, and application thereof in acetylene hydrochlorination reaction. Background Art
[0002] Polyvinyl chloride (PVC) is the world's second largest general-purpose plastic. It is inexpensive and has superior comprehensive properties. It is widely used in building materials, packaging, electronics, daily consumer goods and other fields. It is the chemical product with the largest output, lowest cost and widest application among the five general-purpose resins.
[0003] The monomer vinyl chloride (VCM) of PVC can be synthesized by multiple process routes, the most commonly used ones are the calcium carbide method and the ethylene method. Foreign crude oil resources are abundant, and the PVC industry mainly uses ethylene produced from petroleum as raw material to synthesize vinyl chloride, without the need for mercury catalysts for catalysis. my country's energy structure is rich in coal, poor in oil and little gas, which leads to the fact that my country's PVC industry mainly uses the coal-to-calcium carbide acetylene method to synthesize vinyl chloride, and the reaction must be carried out under the catalytic conditions of mercury catalysts. However, mercury catalysts can cause mercury pollution and endanger human health.
[0004] At present, the research direction of mercury-free catalysts for acetylene hydrochlorination is mainly precious metal-based catalysts. Although most precious metal-based catalysts have advantages such as high catalytic activity and good selectivity, due to the high impurities in the raw gas and the presence of reducing components (such as H 2 , H 2 S. PH 3 NH 3 ) exist, there are problems such as rapid inactivation and insufficient stability in application experiments. Summary of the invention
[0005] In view of this, the object of the present invention is to provide an aryl phosphine oxide ligand copper-based catalyst and a preparation method thereof and application in acetylene hydrochlorination reaction. The aryl phosphine oxide ligand copper-based catalyst provided by the present invention is used for preparing vinyl chloride by acetylene hydrochlorination, and not only has high acetylene conversion rate and high vinyl chloride selectivity, but also is not easy to deactivate and has good stability.
[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:
[0007] The present invention provides an aryl phosphine oxide ligand copper-based catalyst, comprising activated carbon and a metal complex supported on the activated carbon;
[0008] The metal complex is composed of an aryl phosphine oxide ligand, a divalent copper salt and a noble metal compound, or the metal complex is composed of an aryl phosphine oxide ligand, a divalent copper salt and an indium-containing compound;
[0009] The aryl phosphine oxide ligand has a structure shown in Formula 1:
[0010]
[0011] In Formula 1, R1 and R2 are independently methyl, ethyl, methoxymethyl, benzyl, allyl, phenyl, mercaptomethyl, 3-bromophenyl, 2,5-dihydroxyphenyl, 4-(hydroxymethyl)phenyl or vinyl, and R1 and R2 are different.
[0012] Preferably, the loading amount of the aryl phosphine oxide ligand in the aryl phosphine oxide ligand copper-based catalyst is 1-10wt%, the loading amount of the divalent copper salt is 1-30wt%, the loading amount of the noble metal compound is 0.1-2wt%, and the loading amount of the indium-containing compound is 0.1-5wt%.
[0013] Preferably, the divalent copper salt comprises copper chloride.
[0014] Preferably, the precious metal compound is a gold-containing compound, a platinum-containing compound, a palladium-containing compound, a silver-containing compound, a rhodium-containing compound or a ruthenium-containing compound.
[0015] Preferably, the gold-containing compound is (triphenylphosphine)gold(I) chloride or (dimethylphenylphosphine)gold chloride;
[0016] The platinum-containing compound is platinum tetrachloride, hexachloroplatinic acid, tetrakis(triphenylphosphine)platinum, acetylacetonate platinum(II) or cis-dichlorobis(pyridine)platinum(II);
[0017] The palladium-containing compound is palladium chloride, palladium nitrate, palladium acetate, palladium sulfate, triphenylphosphine palladium acetate, bis(cyanobenzene)palladium dichloride, tetrakis(triphenylphosphine)palladium or bis(triphenylphosphine)palladium(II) chloride;
[0018] The silver-containing compound is silver sulfadiazine;
[0019] The rhodium-containing compound is rhodium (III) iodide, rhodium trichloride hydrate, rhodium (III) bromide, triphenylphosphine rhodium chloride, tetrakis (triphenylacetic acid) dirhodium, tetrakis (triphenylphosphine) rhodium hydride (I), tetracarbonyl dirhodium dichloride or bis (1,5-cyclooctadiene) rhodium tetrafluoroborate;
[0020] The ruthenium-containing compound is ruthenium trichloride, ruthenium (III) bromide, ruthenium (III) iodide, ruthenium (III) acetylacetonate, triruthenium dodecacarbonyl, tri(triphenylphosphine) dichloride of ruthenium or bis(ethylcyclopentadiene) ruthenium (II).
[0021] Preferably, the indium-containing compound is indium chloride, indium sulfate, indium fluoroborate, indium trifluoromethanesulfonate, tris(2,4-pentanedione)indium(III) or tris(2,2,6,6-tetramethyl-3,5-heptanedione)indium(III).
[0022] Preferably, the activated carbon is coconut shell activated carbon.
[0023] The present invention provides a method for preparing the aryl phosphine oxide ligand copper-based catalyst described in the above scheme, comprising the following steps: mixing a volatile organic solvent, a divalent copper salt and an aryl phosphine oxide ligand until no solid matter is present, to obtain an intermediate complex solution;
[0024] Adding a noble metal compound or an indium-containing compound to the intermediate complex solution until no solid matter is present, thereby obtaining a metal complex solution;
[0025] The activated carbon is mixed with the metal complex solution, and the volatile organic solvent is removed and then dried to obtain the aryl phosphine oxide ligand copper-based catalyst.
[0026] Preferably, the volatile organic solvent comprises ethanol and / or dichloromethane.
[0027] The present invention provides the use of the aryl phosphine oxide ligand copper-based catalyst described in the above scheme or the aryl phosphine oxide ligand copper-based catalyst prepared by the preparation method described in the above scheme in acetylene chlorination reaction.
[0028] The invention provides an aryl phosphine oxide ligand copper-based catalyst, comprising activated carbon and a metal complex supported on the activated carbon; the metal complex is composed of an aryl phosphine oxide ligand, a divalent copper salt and a noble metal compound, or the metal complex is composed of an aryl phosphine oxide ligand, a divalent copper salt and an indium-containing compound.
[0029] In the present invention, the addition of copper and noble metals (or indium) plays a synergistic catalytic role. Compared with the complementary catalytic performance of each individual component, this combined effect significantly enhances or improves the catalytic performance, inhibits the reduction process of the noble metal (or indium), promotes the noble metal (or indium) to maintain a high-valence state, and maintains the catalytic activity, selectivity and catalyst life.
[0030] The aromatic phosphine oxide ligand has a phosphorus-containing group with a lone pair of electrons, which acts as an electron donor and improves the anchoring effect between the metal species and the activated carbon support. At the same time, it forms a metal coordination bond with copper and noble metals (or indium), promotes the transfer of electrons from heteroatoms to copper and noble metal ions (or indium ions), and prevents excessive reduction and deactivation of metal species.
[0031] Furthermore, the precious metal compounds of the present invention are partially organic metal compounds, in which chemical bonds exist between metal atoms and carbon atoms. Since the carbon-metal bond has the properties of a polar covalent bond, such metal organic compounds have the properties of a covalent compound. The metal atom is not surrounded by an 8-electron saturated stable structure, but has a tendency to form dimers or accept electron pairs to achieve a saturated stable structure, which can prevent excessive reduction and inactivation of precious metal species.
[0032] In addition, compared with existing noble metal-based catalysts (reaction temperature is generally 180°C), the catalyst of the present invention has the advantage of low reaction temperature when used for acetylene hydrochlorination to prepare vinyl chloride, and also exhibits good catalytic performance under conditions less than 180°C (such as 100-150°C).
[0033] The present invention provides a method for preparing the aryl phosphine oxide ligand copper-based catalyst described in the above scheme, which has simple operation and low preparation cost. DETAILED DESCRIPTION
[0034] The invention provides an aryl phosphine oxide ligand copper-based catalyst, comprising activated carbon and a metal complex supported on the activated carbon.
[0035] In the present invention, the activated carbon is preferably coconut shell activated carbon. The present invention uses activated carbon as a catalyst carrier, which has the advantages of wide sources and low prices, and the activated carbon has a large specific surface area, which can increase the contact area between active species and acetylene gas.
[0036] In the present invention, the metal complex is composed of an aryl phosphine oxide ligand, a divalent copper salt and a noble metal compound, or the metal complex is composed of an aryl phosphine oxide ligand, a divalent copper salt and an indium-containing compound.
[0037] In the present invention, the aryl phosphine oxide ligand has a structure shown in Formula 1:
[0038]
[0039] In Formula 1, R1 and R2 are independently methyl, ethyl, methoxymethyl, benzyl, allyl, phenyl, mercaptomethyl, 3-bromophenyl, 2,5-dihydroxyphenyl, 4-(hydroxymethyl)phenyl or vinyl, and R1 and R2 are different; preferably, R1 is phenyl, and R2 is methyl, ethyl, methoxymethyl, benzyl, allyl, mercaptomethyl, 3-bromophenyl, 2,5-dihydroxyphenyl, 4-(hydroxymethyl)phenyl or vinyl; in a specific embodiment, the aryl phosphine oxide ligand can be ethyldiphenylphosphine oxide, (mercaptomethyl)diphenylphosphine oxide, (3-bromophenyl)diphenylphosphine oxide, methoxymethyl (diphenyl)phosphine oxide, (4-(hydroxymethyl)phenyl)diphenylphosphine oxide or allyldiphenylphosphine oxide or methyldiphenylphosphine oxide.
[0040] In the present invention, the loading amount of the aryl phosphine oxide ligand in the aryl phosphine oxide ligand copper-based catalyst is preferably 1-10wt%, and in specific embodiments can be 1wt%, 3wt%, 5wt%, 8wt% or 10wt%. In the present invention, the aryl phosphine oxide ligand has a phosphorus-containing group with a lone pair of electrons, which acts as an electron donor, improves the anchoring effect between copper and the activated carbon carrier, and at the same time, it forms a metal coordination bond with copper, promotes the transfer of electrons from heteroatoms to copper and noble metal ions (or indium ions), and prevents excessive reduction and deactivation of metal species.
[0041] In the present invention, the divalent copper salt preferably includes copper chloride. The loading amount of the divalent copper salt in the arylphosphine oxide ligand copper-based catalyst is preferably 1 to 30 wt%, and in specific embodiments can be 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt%. In the present invention, divalent copper is used as an active component.
[0042] In the present invention, the noble metal compound is preferably a gold-containing compound, a platinum-containing compound, a palladium-containing compound, a silver-containing compound, a rhodium-containing compound or a ruthenium-containing compound.
[0043] Wherein, the gold-containing compound is preferably (triphenylphosphine)gold(I) chloride or (dimethylphenylphosphine)gold chloride;
[0044] The platinum-containing compound is preferably platinum tetrachloride, hexachloroplatinic acid, tetrakis(triphenylphosphine)platinum, acetylacetonate platinum(II) or cis-dichlorobis(pyridine)platinum(II);
[0045] The palladium-containing compound is preferably palladium chloride, palladium nitrate, palladium acetate, palladium sulfate, triphenylphosphine palladium acetate, bis(cyanobenzene)palladium dichloride, tetrakis(triphenylphosphine)palladium or bis(triphenylphosphine)palladium(II) chloride;
[0046] The silver-containing compound is preferably silver sulfadiazine;
[0047] The rhodium-containing compound is preferably rhodium (III) iodide, rhodium trichloride hydrate, rhodium (III) bromide, triphenylphosphine rhodium chloride, tetrakis (triphenylacetic acid) dirhodium, tetrakis (triphenylphosphine) rhodium hydride (I), tetracarbonyl dirhodium dichloride or bis (1,5-cyclooctadiene) rhodium tetrafluoroborate;
[0048] The ruthenium-containing compound is preferably ruthenium trichloride, ruthenium (III) bromide, ruthenium (III) iodide, ruthenium (III) acetylacetonate, triruthenium dodecacarbonyl, tris(triphenylphosphine)dichloride or bis(ethylcyclopentadiene)ruthenium (II).
[0049] In the present invention, the loading amount of the noble metal compound in the arylphosphine oxide ligand copper-based catalyst is preferably 0.1-2wt%, and in specific embodiments can be 0.1wt%, 0.5wt%, 0.8wt%, 1wt%, 1.2wt%, 1.5wt% or 2wt%. In the present invention, the noble metal is used as an active component.
[0050] In the present invention, the indium-containing compound is preferably indium chloride, indium sulfate, indium fluoroborate, indium trifluoromethanesulfonate, tris(2,4-pentanedione)indium(III) or tris(2,2,6,6-tetramethyl-3,5-heptanedione)indium(III). The loading amount of the indium-containing compound in the aryl phosphine oxide ligand copper-based catalyst is preferably 0.1-5wt%, and in a specific embodiment it can be 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt% or 5wt%. In the present invention, indium is used as an active component.
[0051] In the present invention, the addition of copper and noble metals (or indium) plays a synergistic catalytic role. Compared with the complementary catalytic performance of each individual component, this combined effect significantly enhances or improves the catalytic performance, inhibits the reduction process of the noble metal (or indium), promotes the noble metal (or indium) to maintain a high-valence state, and maintains the catalytic activity, selectivity and catalyst life.
[0052] In addition, the precious metal catalyst used in the present invention is partly an organic metal compound, and there is a chemical bond between the precious metal atom and the carbon atom. Since the carbon-metal bond has the properties of a polar covalent bond, this type of metal organic compound has the properties of a covalent compound. The metal atom is not surrounded by an 8-electron saturated stable structure, and has a tendency to form a dimer or accept electron pairs to achieve a saturated stable structure, which can prevent excessive reduction and inactivation of the precious metal species.
[0053] The present invention provides a method for preparing the aryl phosphine oxide ligand copper-based catalyst described in the above scheme, comprising the following steps: mixing a volatile organic solvent, a divalent copper salt and an aryl phosphine oxide ligand until no solid matter is present, to obtain an intermediate complex solution;
[0054] Adding a noble metal compound or an indium-containing compound to the intermediate complex solution until no solid matter is present, thereby obtaining a metal complex solution;
[0055] The activated carbon is mixed with the metal complex solution, and the volatile organic solvent is removed and then dried to obtain the aryl phosphine oxide ligand copper-based catalyst.
[0056] In the present invention, unless otherwise specified, the raw materials used are commercially available products well known in the art.
[0057] The invention mixes a volatile organic solvent, a divalent copper salt and an aryl phosphine oxide ligand until no solid matter exists, thereby obtaining an intermediate complex solution.
[0058] In the present invention, the volatile organic solvent preferably includes ethanol and / or dichloromethane; when the volatile solvent is ethanol and dichloromethane, the volume ratio of ethanol to dichloromethane is preferably 1: (0.5-1), and in a specific embodiment it can be 1: 0.5 or 1: 1. The present invention has no special requirements for the amount of the volatile organic solvent, as long as it can completely dissolve the divalent copper salt and the aryl phosphine oxide ligand and the complex formed by the two.
[0059] In the present invention, the mixing is preferably carried out under stirring and room temperature (without additional heating or cooling). During the mixing process, the divalent copper salt and the aryl phosphine oxide ligand are first dissolved and then coordinated. In the present invention, after the solution is preferably observed to be clear, the next step can be carried out.
[0060] After obtaining the intermediate complex solution, the present invention adds a noble metal compound or an indium-containing compound to the intermediate complex solution until no solid matter exists, thereby obtaining a metal complex solution.
[0061] The present invention preferably performs ultrasound after adding the noble metal compound or the indium-containing compound; the ultrasound time is preferably 10 to 60 minutes, and in specific embodiments it can be 10 minutes, 30 minutes, 40 minutes or 60 minutes. The present invention promotes the dissolution and coordination reaction of the noble metal compound (or the indium-containing compound) by ultrasound.
[0062] After obtaining the metal complex solution, the present invention mixes the activated carbon with the metal complex solution, removes the volatile organic solvent and then dries to obtain the aryl phosphine oxide ligand copper-based catalyst.
[0063] In the present invention, the activated carbon is preferably coconut shell activated carbon; the coconut shell activated carbon preferably meets the requirements of particle size and mechanical strength in GB / T31530-2015; specifically, the particle size Φ of the coconut shell activated carbon is (3mm-6mm)×(3mm-8mm), the attrition rate ω / %≥95, the mechanical strength ≥95%, the ash content is less than 3%, and the total specific surface area is greater than 1200m 2 / g, and the iodine value is greater than 1100 mg / g. In the embodiment of the present invention, the coconut shell activated carbon is a commercially available product that meets the above requirements.
[0064] In the present invention, the mixing of the activated carbon and the metal complex solution is preferably: adding the activated carbon to the metal complex solution and stirring. The present invention has no special requirements for the stirring, and it only needs to be stirred evenly.
[0065] In the present invention, the removal of volatile organic solvents is preferably carried out by natural placement. The present invention does not specifically limit the time of natural placement, and it can be carried out until the volatile organic solvent is completely evaporated. The preferred scheme is natural placement for 7 to 14 days. In the process of natural placement of the present invention, the organic solvent gradually evaporates, and the metal complex is combined with the activated carbon. In the present invention, the longer the natural placement time is, the better the catalytic performance of the obtained aromatic phosphine oxide ligand copper-based catalyst.
[0066] The present invention does not specifically limit the drying conditions, and well-known drying conditions may be used. In the embodiment of the present invention, the drying is performed at 120° C. for 4 hours.
[0067] The present invention provides the use of the aryl phosphine oxide ligand copper-based catalyst described in the above scheme or the aryl phosphine oxide ligand copper-based catalyst prepared by the preparation method described in the above scheme in acetylene chlorination reaction.
[0068] In the present invention, the raw materials for the acetylene chlorination reaction preferably include acetylene and hydrogen chloride; the molar ratio of acetylene to hydrogen chloride is preferably 1:(1-1.5), and in specific embodiments can be 1:1, 1:1.1, 1:1.3 or 1:1.5; the spatial flow rate of acetylene is preferably 10-500h -1 In a specific embodiment, it can be 10h -1 , 50h -1 , 100h -1 , 150h -1 , 200h -1 、300h -1 , 400h -1 or 500h -1 .
[0069] In the present invention, the temperature of the acetylene chlorination reaction is preferably 100-180°C, and in specific embodiments may be 100°C, 120°C, 150°C, 160°C or 180°C.
[0070] The aryl phosphine oxide ligand copper-based catalyst provided by the present invention, its preparation method and its application in acetylene hydrochlorination reaction are described in detail below in conjunction with the examples, but they should not be construed as limiting the scope of protection of the present invention.
[0071] Example 1
[0072] (1) dissolving copper chloride and ethyl diphenyl phosphine oxide in 20 mL of ethanol at room temperature in a beaker, and stirring evenly until the solution is clear to the bottom, thereby obtaining an intermediate complex solution;
[0073] (2) adding indium sulfate to the intermediate complex solution obtained in step (1), and performing ultrasonic dissolution treatment for 10 min until the solution is clear to the bottom, thereby obtaining a metal complex solution;
[0074] (3) Add coconut shell activated carbon to the metal complex solution obtained in step (2) and continue stirring. Stir evenly and place for 14 days until the solvent evaporates naturally. Dry in an oven at 120° C. for 4 h to obtain an aromatic phosphine oxide ligand copper-based catalyst (referred to as the finished catalyst).
[0075] The weight percentages of cupric chloride, ethyl diphenyl phosphine oxide, indium sulfate and coconut shell activated carbon in the finished catalyst are 25%, 7%, 1% and 67% respectively.
[0076] Example 2
[0077] (1) Dissolve copper chloride and (mercaptomethyl)diphenylphosphine oxide in 10 mL of ethanol and 10 mL of dichloromethane at room temperature in a beaker, and stir evenly until the solution is clear to the bottom, thereby obtaining an intermediate complex solution;
[0078] (2) adding (dimethylphenylphosphine)gold chloride to the intermediate complex solution obtained in step (1), and ultrasonically dissolving the solution for 30 minutes until the solution is clear to the bottom, thereby obtaining a metal complex solution;
[0079] (3) Add coconut shell activated carbon to the metal complex solution obtained in step (2) and continue stirring. Stir evenly and place for 14 days until the solvent evaporates naturally. Dry in an oven at 120° C. for 4 h to obtain an aromatic phosphine oxide ligand copper-based catalyst.
[0080] The weight percentages of cupric chloride, (mercaptomethyl) diphenylphosphine oxide, (dimethylphenylphosphine) gold chloride and coconut shell activated carbon in the finished catalyst are 15%, 10%, 1% and 74% respectively.
[0081] Example 3
[0082] (1) Dissolve copper chloride and (3-bromophenyl)diphenylphosphine oxide in 10 mL of ethanol and 10 mL of dichloromethane at room temperature in a beaker, and stir evenly until the solution is clear to the bottom, thereby obtaining an intermediate complex solution;
[0083] (2) adding triphenylphosphine palladium acetate to the intermediate complex solution obtained in step (1), and ultrasonically dissolving the solution for 20 minutes until the solution is clear to the bottom, thereby obtaining a metal complex solution;
[0084] (3) Add coconut shell activated carbon to the metal complex solution obtained in step (2) and continue stirring. Stir evenly and place for 14 days until the solvent evaporates naturally. Dry in an oven at 120° C. for 4 h to obtain an aromatic phosphine oxide ligand copper-based catalyst.
[0085] The weight percentages of cupric chloride, (3-bromophenyl) diphenylphosphine oxide, triphenylphosphine palladium acetate and coconut shell activated carbon in the finished catalyst are 20%, 10%, 1% and 69% respectively.
[0086] Example 4
[0087] (1) Dissolve copper chloride and methoxymethyl (diphenyl) phosphine oxide in 10 mL of ethanol and 10 mL of dichloromethane at room temperature in a beaker, and stir evenly until the solution is clear to the bottom, thereby obtaining an intermediate complex solution;
[0088] (2) adding ruthenium chloride to the intermediate complex solution obtained in step (1), and dissolving by ultrasonic treatment for 20 minutes until the solution is clear to the bottom, thereby obtaining a metal complex solution;
[0089] (3) Add coconut shell activated carbon to the metal complex solution obtained in step (2) and continue stirring. Stir evenly and place for 7 days until the solvent evaporates naturally. Dry in an oven at 120° C. for 4 h to obtain an aromatic phosphine oxide ligand copper-based catalyst.
[0090] The weight percentages of cupric chloride, methoxymethyl (diphenyl) phosphine oxide, ruthenium chloride and coconut shell activated carbon in the finished catalyst are 2%, 10%, 1.5% and 86.5% respectively.
[0091] Example 5
[0092] (1) Dissolve copper chloride and (4-(hydroxymethyl)phenyl)diphenylphosphine oxide in 20 mL of ethanol at room temperature in a beaker, and stir evenly until the solution is clear to the bottom, thereby obtaining an intermediate complex solution;
[0093] (2) adding platinum tetrachloride to the intermediate complex solution obtained in step (1), and dissolving by ultrasonic treatment for 10 min until the solution is clear to the bottom, thereby obtaining a metal complex solution;
[0094] (3) Add coconut shell activated carbon to the metal complex solution obtained in step (2) and continue stirring. Stir evenly and place for 14 days until the solvent evaporates naturally. Dry in an oven at 120° C. for 4 h to obtain an aromatic phosphine oxide ligand copper-based catalyst.
[0095] The weight percentages of cupric chloride, (4-(hydroxymethyl) theoyl) diphenylphosphine oxide, platinum tetrachloride and coconut shell activated carbon in the finished catalyst are 8%, 10%, 0.5% and 81.5% respectively.
[0096] Example 6
[0097] (1) Dissolve copper chloride and allyl diphenylphosphine oxide in 10 mL of ethanol and 10 mL of dichloromethane at room temperature in a beaker, and stir evenly until the solution is clear to the bottom, thereby obtaining an intermediate complex solution;
[0098] (2) adding hydrated rhodium trichloride to the intermediate complex solution obtained in step (1), and dissolving by ultrasonic treatment for 30 minutes until the solution is clear to the bottom, thereby obtaining a metal complex solution;
[0099] (3) Add coconut shell activated carbon to the metal complex solution obtained in step (2) and continue stirring. Stir evenly and place for 14 days until the solvent evaporates naturally. Dry in an oven at 120° C. for 4 h to obtain an aromatic phosphine oxide ligand copper-based catalyst.
[0100] The weight percentages of cupric chloride, allyl diphenyl phosphine oxide, hydrated rhodium trichloride and coconut shell activated carbon in the finished catalyst are 20%, 2%, 1% and 77% respectively.
[0101] Comparative Example 1
[0102] The difference from Example 2 is that the noble metal compound (dimethylphenylphosphine) gold chloride is omitted, and the specific steps are as follows:
[0103] (1) Dissolve copper chloride and (mercaptomethyl)diphenylphosphine oxide in 10 mL of ethanol and 10 mL of dichloromethane at room temperature in a beaker, and stir evenly until the solution is clear to the bottom, thereby obtaining a metal complex solution;
[0104] (2) Add coconut shell activated carbon to the intermediate complex solution obtained in step (1) and continue stirring. Stir evenly and place for 14 days until the solvent evaporates naturally. Dry in an oven at 120° C. for 4 h to obtain an aromatic phosphine oxide ligand copper-based catalyst.
[0105] The weight percentages of cupric chloride, (mercaptomethyl)diphenylphosphine oxide and coconut shell activated carbon in the finished catalyst are 15%, 10% and 75% respectively.
[0106] Comparative Example 2
[0107] The difference from Example 2 is that (mercaptomethyl)diphenylphosphine oxide is omitted, and the specific steps are as follows:
[0108] (1) Dissolve copper chloride and (dimethylphenylphosphine) gold chloride in 10 mL of ethanol and 10 mL of dichloromethane at room temperature in a beaker and stir until the solution is clear.
[0109] (2) Add coconut shell activated carbon to the solution obtained in step (1) and continue stirring. Stir evenly and place for 14 days until the solvent evaporates naturally. Dry in an oven at 120° C. for 4 h to obtain a catalyst.
[0110] The weight percentages of cupric chloride, (dimethylphenylphosphine) gold chloride and coconut shell activated carbon in the finished catalyst are 15%, 1% and 84% respectively.
[0111] Comparative Example 3
[0112] The difference from Example 2 is that cupric chloride is omitted, and the specific steps are as follows:
[0113] (1) Dissolve (mercaptomethyl)diphenylphosphine oxide and (dimethylphenylphosphine)gold chloride in 10 mL of ethanol and 10 mL of dichloromethane at room temperature in a beaker, and stir evenly until the solution is clear to the bottom, thereby obtaining a metal complex solution;
[0114] (2) Add coconut shell activated carbon to the complex solution obtained in step (1) and continue stirring. Stir evenly, place for 14 days until the solvent evaporates naturally, and dry in an oven at 120° C. for 4 hours to obtain an aryl phosphine oxide ligand copper-based catalyst. The weight percentages of (mercaptomethyl) diphenyl phosphine oxide, (dimethylphenylphosphine) gold chloride, and coconut shell activated carbon in the finished catalyst are 10%, 1%, and 89%, respectively.
[0115] Catalytic performance test:
[0116] The catalysts of Examples 1 to 6 and Comparative Examples 1 to 3 were used for the catalytic reaction of acetylene hydrochlorination, and the specific steps were as follows: before entering the fixed reactor, the nitrogen, acetylene and hydrogen chloride gas were dried to remove moisture and hydrogen sulfide, and the acetylene flow rate and hydrogen chloride flow rate were controlled by a mass flow meter. Before the reaction, nitrogen was introduced for purging for 0.5 h, then switched to hydrogen chloride gas for activation at 150°C for 0.5 h, and then switched to a mixed gas of acetylene and hydrogen chloride for reaction, the reaction temperature was controlled to be 150°C, the molar ratio of acetylene to hydrogen chloride was 1:1.1, and the acetylene space flow rate was 50 h -1 The reaction product was passed into an absorption bottle and a drying bottle and then into a gas chromatograph for analysis. The conversion rate and selectivity for 2 hours and the decrease rate for 50 hours are shown in Table 1.
[0117] Table 1 Catalyst compositions and catalytic results of the examples and comparative examples
[0118]
[0119] Note: The decreasing rate of reaction for 50 hours in Table 1 refers to the decreasing value of acetylene conversion rate after reaction for 50 hours compared with reaction for 2 hours. For example, the decreasing rate of reaction for 50 hours in Example 1 is 0.8%, which means that the acetylene conversion rate decreases to 97.5%-0.8%=96.7% after reaction for 50 hours.
[0120] From the results in Table 1, it can be seen that the aryl phosphine oxide ligand copper-based catalyst prepared by the present invention has a high acetylene conversion rate and a high vinyl chloride selectivity. After the noble metal compound, aryl phosphine oxide ligand and copper chloride are omitted in Comparative Examples 1 to 3, the activity of the obtained catalysts is significantly reduced, indicating that the three types of copper dichloride, aryl phosphine oxide ligand and noble metal catalyst cooperate with each other to improve the catalytic activity of the catalyst.
[0121] In addition, the faster the decrease rate after 50h of reaction, the more unstable the catalyst is. From the results in Table 1, it can be seen that the acetylene conversion rate of the aryl phosphine oxide ligand copper-based catalyst prepared by the present invention decreases by less than 1.5% after 50h of reaction compared with 2h, indicating that the catalyst of the present invention has good stability.
[0122] It can be seen from the above embodiments that the present invention provides an aryl phosphine oxide ligand copper-based catalyst and a preparation method thereof and an application thereof in an acetylene hydrochlorination reaction. The aryl phosphine oxide ligand copper-based catalyst provided by the present invention is used for preparing vinyl chloride by acetylene hydrochlorination, and not only has a high acetylene conversion rate and high vinyl chloride selectivity, but is also not easily deactivated and has good stability.
[0123] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. An aromatic phosphine oxide ligand copper-based catalyst, characterized in that: It includes activated carbon and a metal complex supported on the activated carbon; The metal complex is composed of an aryl phosphine oxide ligand, a divalent copper salt and a noble metal compound, or the metal complex is composed of an aryl phosphine oxide ligand, a divalent copper salt and an indium-containing compound; The aryl phosphine oxide ligand has a structure shown in Formula 1: In Formula 1, R1 and R2 are independently methyl, ethyl, methoxymethyl, benzyl, allyl, phenyl, mercaptomethyl, 3-bromophenyl, 2,5-dihydroxyphenyl, 4-(hydroxymethyl)phenyl or vinyl, and R1 and R2 are different.
2. The aryl phosphine oxide ligand copper-based catalyst according to claim 1, characterized in that: In the aryl phosphine oxide ligand copper-based catalyst, the loading amount of the aryl phosphine oxide ligand is 1-10 wt %, the loading amount of the divalent copper salt is 1-30 wt %, the loading amount of the noble metal compound is 0.1-2 wt %, and the loading amount of the indium-containing compound is 0.1-5 wt %.
3. The aryl phosphine oxide ligand copper-based catalyst according to claim 1 or 2, characterized in that: The divalent copper salt includes copper chloride.
4. The aryl phosphine oxide ligand copper-based catalyst according to claim 1 or 2, characterized in that: The noble metal compound is a gold-containing compound, a platinum-containing compound, a palladium-containing compound, a silver-containing compound, a rhodium-containing compound or a ruthenium-containing compound.
5. The aryl phosphine oxide ligand copper-based catalyst according to claim 4, characterized in that: The gold-containing compound is (triphenylphosphine)gold(I) chloride or (dimethylphenylphosphine)gold chloride; The platinum-containing compound is platinum tetrachloride, hexachloroplatinic acid, tetrakis(triphenylphosphine)platinum, acetylacetonate platinum(II) or cis-dichlorobis(pyridine)platinum(II); The palladium-containing compound is palladium chloride, palladium nitrate, palladium acetate, palladium sulfate, triphenylphosphine palladium acetate, bis(cyanobenzene)palladium dichloride, tetrakis(triphenylphosphine)palladium or bis(triphenylphosphine)palladium(II) chloride; The silver-containing compound is silver sulfadiazine; The rhodium-containing compound is rhodium (III) iodide, rhodium trichloride hydrate, rhodium (III) bromide, triphenylphosphine rhodium chloride, tetrakis (triphenylacetic acid) dirhodium, tetrakis (triphenylphosphine) rhodium hydride (I), tetracarbonyl dirhodium dichloride or bis (1,5-cyclooctadiene) rhodium tetrafluoroborate; The ruthenium-containing compound is ruthenium trichloride, ruthenium (III) bromide, ruthenium (III) iodide, ruthenium (III) acetylacetonate, triruthenium dodecacarbonyl, tri(triphenylphosphine) dichloride of ruthenium or bis(ethylcyclopentadiene) ruthenium (II).
6. The aryl phosphine oxide ligand copper-based catalyst according to claim 1 or 2, characterized in that: The indium-containing compound is indium chloride, indium sulfate, indium fluoroborate, indium trifluoromethanesulfonate, tris(2,4-pentanedione)indium(III) or tris(2,2,6,6-tetramethyl-3,5-heptanedione)indium(III).
7. The aryl phosphine oxide ligand copper-based catalyst according to claim 1, characterized in that: The activated carbon is coconut shell activated carbon.
8. A method for preparing the arylphosphine oxide ligand copper-based catalyst according to any one of claims 1 to 7, comprising the following steps: Mixing a volatile organic solvent, a divalent copper salt and an arylphosphine oxide ligand until no solid matter is present, to obtain an intermediate complex solution; Adding a noble metal compound or an indium-containing compound to the intermediate complex solution until no solid matter is present, thereby obtaining a metal complex solution; The activated carbon is mixed with the metal complex solution, and the volatile organic solvent is removed and then dried to obtain the aryl phosphine oxide ligand copper-based catalyst.
9. The preparation method according to claim 8, characterized in that: The volatile organic solvent includes ethanol and / or dichloromethane.
10. Use of the aryl phosphine oxide ligand copper-based catalyst according to any one of claims 1 to 7 or the aryl phosphine oxide ligand copper-based catalyst prepared by the preparation method according to any one of claims 8 to 9 in acetylene chlorination reaction.