CN114524729A - Application of carbon-supported monatomic Pd catalyst in alkyne carbonylation reaction - Google Patents

Application of carbon-supported monatomic Pd catalyst in alkyne carbonylation reaction Download PDF

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CN114524729A
CN114524729A CN202011320908.2A CN202011320908A CN114524729A CN 114524729 A CN114524729 A CN 114524729A CN 202011320908 A CN202011320908 A CN 202011320908A CN 114524729 A CN114524729 A CN 114524729A
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冯四全
丁云杰
宋宪根
李星局
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Dalian Institute of Chemical Physics of CAS
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Abstract

An application of a carbon-carried monatomic Pd catalyst in alkyne dicarbonylation reaction. The method is characterized in that Pd in the catalyst is in the form of mononuclear complex of carbonyl iodide, and a single atom is anchored on the surface of a carbon carrier containing a coordination group N, O, P, S. Under certain reaction conditions, C2nH2n、CO、O2And alcohol ROH or water H2Can carry out double carbonylation reaction with high activity and high selectivity in the presence of O to generate olefin diacid and olefin di-acid with more than two carbon atomsAn acid ester. The catalyst is applied to alkyne double carbonylation reaction and has good catalytic activity and stability.

Description

Application of carbon-supported monatomic Pd catalyst in alkyne carbonylation reaction
Technical Field
The invention belongs to the technical field of catalytic chemical engineering, and particularly relates to an application of a carbon-supported monatomic Pd catalyst in an alkyne carbonylation reaction.
Background
Among industrial catalysts, supported metal catalysts account for more than 70%, and particularly supported noble metal catalysts are widely used for various catalyst reactions. In the actual industrial production, the supported metal catalyst is usually a nano metal catalyst, and only atoms exposed on the surface have catalyst activity, so that the utilization efficiency of metal atoms is low, and the precious metal resources are wasted.
Compared with nano metal catalysts, the single atom catalyst becomes an emerging hotspot of contemporary research due to the nearly 100% atom utilization rate and the single catalytic active site.
Using CO and CH3I, carrying out monodisperse heat treatment on the supported nano metal particles, and carrying out in-situ atomic-level monodisperse on the supported nano metal particles so as to prepare the carbon-supported monatomic Pd catalyst.
Acetylene of the formula C2H2The material is called acetylene, and is an important organic synthetic raw material, and is called the 'industrial mother material for organic synthesis'. The calcium carbide can be easily prepared by adding water, and the Xinjiang area in China has abundant calcium carbide and can produce a large amount of acetylene. Other alkynes can be selectively prepared by utilizing acetylene, thereby enriching the large-scale and upstream and downstream product utilization of the alkynes.
Taking acetylene as an example, acetylene is polymerized under certain conditions to generate aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, anthracene, styrene, indene and the like. By substitution and addition reactions, a series of extremely valuable products can be produced. For example, acetylene is dimerized to produce vinyl acetylene, which is further subjected to an addition reaction with hydrogen chloride to produce chloroprene; preparing acetaldehyde by direct hydration of acetylene; acetylene and hydrogen chloride are subjected to addition reaction to prepare chloroethylene; acetylene reacts with acetic acid to prepare vinyl acetate; reacting acetylene with hydrogen cyanide to prepare acrylonitrile; acetylene reacts with ammonia to produce picoline and 2-methyl-5-ethylpyridine; acetylene reacts with toluene to produce xylylethylene, and further the catalyst is cracked to produce three isomers of methylstyrene: acetylene is condensed with one molecule of formaldehyde to form propiolic alcohol, and is condensed with two molecules of formaldehyde to form butynediol; acetylene and acetone are subjected to addition reaction to prepare methyl alkynol, and further the methyl alkynol is reacted to generate isoprene; acetylene reacts with carbon monoxide and other compounds (such as water, alcohol, mercaptan) to produce acrylic acid and its derivatives.
In addition, acetylene downstream fine chemicals are a direction of the chemical development of acetylene and other alkynes, and can push the development of modern acetylene chemical products to the depth direction. Alkyne and CO are used as raw materials, and alkyne carbonylation reaction can occur under attack of nucleophilic reagent.
Among them, the carbonylation of acetylene to produce acrylic acid and esters is a typical example of commercial application. However, most of these studies are homogeneous catalysis, and the research focus is mainly on the field of catalysts, and [ Ni (CO) ]4]，[Co(CO)4]2，Fe(CO)5And Pd catalyst system, which is mainly used for homogeneous catalytic reaction to prepare acrylic acid and acrylic ester thereof. By using a Pd catalytic system, the selectivity of the product can be modulated under the action of concentrated sulfuric acid, sulfonic acid and the like by introducing a nitrogen-oxygen ligand, so as to produce products such as butenedioic ester, succinate, maleic anhydride and the like.
In conclusion, the existing acetylene carbonylation mainly has the following problems: (1) the catalyst is basically a homogeneous phase catalytic system, and has the problems of easy loss of the catalyst and difficult separation of products; (2) taking acetylene as an example, most products are acrylic acid and acrylate, and research and development of other alkynes are less; (3) the catalyst has large dosage and low efficiency. The minority of supported metal catalysts are also metal nano metal catalysts, and the utilization rate of metal atoms is low.
Disclosure of Invention
The technical scheme of the invention is as follows: the N, O, P, S modified carbon-supported monatomic Pd catalyst and the application thereof in the double carbonylation of acetylene and other alkynes are provided, the process is novel and simple, the condition is mild, the reaction activity is good, the product selectivity is high, the stability is strong, the yield can reach more than 90 percent, and the catalyst has higher technical competitive advantage. Under certain reaction conditions and the
The specific scheme is the application of the carbon-supported monatomic Pd catalyst in the alkyne dicarbonylation reaction; characterized in that the metal Pd in the catalyst is a mononuclear containing carbonyl and iodine ligandIn the form of a complex, monoatomic dispersion is carried out on the surface of one or more anchored carbon supports containing the coordinating groups N, O, P, S. The content percentage of the metal in the carbon-based carrier is 0.1-5%, preferably 0.1-3%; under certain reaction conditions, C2nH2n、CO、O2And alcohol or water to produce olefin diacid and olefin diacid ester with two more carbons through active and high-selectivity double carbonylation reaction.
Pd in the catalyst is anchored on the oxygen, nitrogen, sulfur and phosphine functional group sites on the carrier in the form of a mononuclear complex of carbonyl halide, and the structural general formula can be represented as follows:
Pd(CO)x M y(O-C，N-C，S-C，P-C)
wherein: O-C, N-C, S-C, P-C respectively represents one or more than two of oxygen, nitrogen, sulfur and phosphine functional groups on the surface of the carbon carrier, x is 1 or 2, y is 1 or 2, and M is one or more than two of Cl, Br and I.
The carbon carrier is coconut shell activated carbon.
The preparation process of the catalyst comprises the following steps: firstly, pretreating a carbon carrier to ensure that the surface of the carbon carrier is rich in N, O, P, S functional groups, then preparing carbon-supported Pd nano metal particles by a method of impregnation, roasting and reduction, and then carrying out monodispersion heat treatment by utilizing CO and halogen, halogen acid or halogenated hydrocarbon to prepare the carbon-supported carbonyl-and halogen-containing coordinated Pd mononuclear complex catalyst.
The carbon support is pretreated so that one or more of the ligands such as N, O, P, S are contained on the carbon support to anchor the mononuclear complex containing the Pd coordinated by a carbonyl group or a halogen. The specific process is as follows: the N-containing group being NH3Introducing a flow tube filled with a carbon carrier for treatment for 2-12 h at 500-900 ℃, or dissolving a porphyrin compound in a corresponding solvent, impregnating the carbon carrier, removing the solvent at 60-80 ℃, and treating for 2-12 h at 300-500 ℃; carrying out oxidation treatment on the O-containing group in a kettle for 2-6 h at the temperature of 200-400 ℃ by using nitric acid; the P-containing group being PCl3Introducing saturated steam at 60-80 ℃ into a flow tube filled with a carbon carrier for treatment for 2-12 h at 500-900 ℃, or dissolving a vinyl triphenylphosphine monomer in tetrahydrofuran, and thenAdding an azodiisobutyronitrile initiator for polymerization, then adding a carbon carrier for impregnation, then drying at 60-80 ℃, then drying again at 100-120 ℃, and processing again at 300-350 ℃; and carrying out reflux treatment on the carbon carrier by adopting S-containing groups at the temperature of 80-100 ℃ by adopting sulfuric acid, or dissolving thiourea and the like in an ether organic solvent, and then adding the carbon carrier for dipping treatment.
The pretreated carbon carrier is loaded with Pd metal by dipping, roasting and H2Is prepared after reduction.
The halogen, halogen acid or halogenated alkane used includes Cl2、Br2、I2Etc. halogen, or HCl, HBr, HI or CH3Cl、CH3Br、CH3CH2Br、CH3CH2CH2Br、CH3I、CH3CH2I、CH3CH2CH2I. One or more than two of iodobenzene; preferably one or more of bromine, iodine, bromide or iodide, and more preferably one or two of iodine or iodide; the halogen, halogen acid or halogenated alkane can be introduced into the reaction system by CO bubbling or by a pump.
The conditions of the monodisperse heat treatment are that the temperature is 100-350 ℃, the pressure is 0.1-3.0 MPa, the molar ratio of CO to (one or more than two of halogen, halogen acid or halogenated hydrocarbon) is 0.1-10, and the treatment time is 10 min-10 h.
The reaction raw materials are alkyne, water or alcohol, CO and O2The reaction conditions are 40-150 ℃ and CO and O2The partial pressure of the reaction is 0.1-5.0 MPa, the mol ratio of alkyne to water or alcohol is 1 (2-10), the mol ratio of alkyne to CO is 1 (1-30), and CO and O are respectively2The molar ratio of (1) to (5).
The use according to claim 8,
the alkyne comprises one or more of acetylene, propine, butyne, pentyne, hexyne, heptyne, octyne, phenylacetylene and the like; the alcohol is one of methanol, ethanol, propanol, butanol, pentanol and octanol.
The reaction is carried out in a kettle type reactor, and the molar ratio of reaction substrate alkyne to Pd in the catalyst is 2000-15000.
Under the carbon-supported monatomic Pd catalyst modified by N, O, P, S, the selectivity of the product can be modulated according to the change of the substrate composition. When the acetic acid acrylic acid is prepared, the reaction substrates comprise acetylene, CO, water and acetic acid, wherein the acetic acid is a solvent; when propionate is prepared, the reaction substrates consist of acetylene, CO and corresponding alcohol; when preparing the butenedioic acid, the reaction components are acetylene, CO, air, water and acetic acid, wherein the acetic acid is a solvent; when the butenedioic ester is prepared, the reaction components comprise acetylene, CO, air and corresponding alcohol. Other alkynes are similar.
The beneficial effects of the patent of the application include but are not limited to:
compared with the prior art, the invention provides an N, O, P, S-modified carbon-supported monatomic Pd catalyst and application thereof in alkyne dicarbonylation reaction. The catalyst Pd used in the technology is a supported single-metal active site Pd catalyst, and belongs to the category of single-atom catalysis. Pd is dispersed on the surface of a carrier modified by functional groups N, O, P, S in an atomic level manner in the form of a mononuclear complex of palladium carbonyl iodide, and the method is applied to carbonylation reactions such as acetylene, and the like, and has the advantages of novel and simple process, mild conditions, good reaction activity, high product selectivity, no need of adding corrosive solvents such as sulfuric acid, hydrochloric acid and the like, no need of adding sulfonic acid, benzenesulfonic acid, paratoluenesulfonic acid and other co-catalysts in the reaction process, equipment corrosion prevention, strong innovation and higher technical competitive advantage.
Drawings
FIG. 1 shows Pd as a sample1Transmission Electron microscopy for/AC.
FIG. 2 shows Pd as a sample1Spherical aberration electron micrograph of/AC.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, all materials and reagents used in the present application were purchased commercially and used as received without treatment, and the equipment used was the manufacturer's recommended protocol and parameters.
In the examples, the transmission electron microscope was used for detection with an instrument of Japanese JEM-2100.
In the embodiment, the spherical aberration electron microscope is detected by using an instrument of Japanese JEM-ARM 200F.
In the embodiment, all catalyst evaluation results adopt an Agilent 7890B liquid chromatograph, an FID detector, a capillary column and an internal standard method to analyze liquid phase composition, and methyl benzoate is used as an internal standard substance;
and calculating according to the composition of each product to obtain the product selectivity.
In the examples of the present application, the acetylene conversion and the product selectivity were calculated based on the carbon mole number of the acetylene converted.
Example 1
Carbon carrier pretreatment: reacting NH3Introducing into a flow tube filled with coconut shell activated carbon, and treating at 800 deg.C for 6 h. 0.17g of PdCl is metered in2Dissolving in 15ml deionized water, adding 10g of treated coconut shell activated carbon, soaking and stirring until no bubbles are generated, evaporating the solvent in a water bath at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, reducing with hydrogen at 300 ℃ for 2h to obtain activated carbon-loaded Pd/AC nano-particles, and then using CO and CH3Treating the mixed gas (molar ratio 1:1) of the I at 100 ℃ for 0.5h to obtain the N modified carbon-supported monatomic Pd catalyst, which is marked as: pd1an/AC-N catalyst. The prepared catalyst is an N-modified carbon-supported monatomic Pd catalyst which can be known by adopting X-ray diffraction XRD, an X-ray absorption fine structure spectrum XAFS, a spherical aberration electron microscope HAADF-STEM and the like.
Example 2
Pre-treating the carbon carrier, namely dissolving porphyrin in ethyl acetate, soaking coconut shell activated carbon, removing the solvent at 60-80 ℃, and treating at 350 ℃ for 6 hours; 0.51g of PdCl is metered in2Dissolving in 15ml deionized water, adding 10g of processed coconut shell carbon, soaking and stirring until no bubbles are generated, evaporating the solvent in a water bath at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, reducing with hydrogen at 300 ℃ for 2h to obtain activated carbon-loaded Pd/AC nano-particles, and then using CO and CH2I2OfTreating the resultant gas (the molar ratio is 0.5:1) at 250 ℃ for 0.5h to obtain the N modified carbon-supported monatomic Pd catalyst, which is marked as follows: pd2an/AC-N catalyst. The prepared catalyst is an N-modified carbon-supported monatomic Pd catalyst which can be known by adopting X-ray diffraction XRD, an X-ray absorption fine structure spectrum XAFS, a spherical aberration electron microscope HAADF-STEM and the like.
Example 3
Pretreatment of a carbon carrier: adding 68% concentrated nitric acid into a small pot at 200-400 ℃, adding coconut shell activated carbon into the small pot for oxidation treatment for 6 hours, and drying at 120 ℃. 0.22g of Pd (NO) is measured3)2Dissolving in 15ml deionized water, adding 10g of processed coconut shell carbon, soaking and stirring until no bubbles are generated, evaporating the solvent in a water bath at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, reducing with hydrogen at 300 ℃ for 2h to obtain activated carbon-loaded Pd/AC nano-particles, and then using CO and CH3Treating the mixed gas of Br (molar ratio 1:1) at 200 ℃ for 2.0h to obtain the O modified carbon-supported monatomic Pd catalyst, which is marked as: pd3an/AC-O catalyst. The prepared catalyst is an N-modified carbon-supported monatomic Pd catalyst which can be known by adopting X-ray diffraction XRD, an X-ray absorption fine structure spectrum XAFS, a spherical aberration electron microscope HAADF-STEM and the like.
Example 4
Pretreatment of a carbon carrier: mixing PCl3Saturated steam at 80 ℃ was introduced into a flow tube containing coconut shell activated carbon and treated at 650 ℃ for 12 h. 0.18g Pd (OAc) was measured2Dissolving in 15ml deionized water, adding 10g of processed coconut shell carbon, soaking and stirring until no bubbles are generated, evaporating the solvent in a water bath at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, reducing with hydrogen at 300 ℃ for 2h to obtain activated carbon-loaded Pd/AC nano-particles, and then adding CO and C2H5The mixed gas of Br (molar ratio 5:1) is treated for 3.0h at 150 ℃ to obtain the P modified carbon-supported monatomic Pd catalyst, which is marked as: pd4an/AC-P catalyst. The prepared catalyst is an N-modified carbon-supported monatomic Pd catalyst which can be known by adopting X-ray diffraction XRD, an X-ray absorption fine structure spectrum XAFS, a spherical aberration electron microscope HAADF-STEM and the like.
Example 5
Pretreatment of a carbon carrier: dissolving vinyl triphenylphosphine monomer inTetrahydrofuran, azodiisobutyronitrile initiator, coconut shell activated carbon, stoving at 60-80 deg.c, stoving at 120 deg.c and treating at 300 deg.c under He protection. 0.85g of PdCl is measured out2Dissolving in 15ml deionized water, adding 10g of processed coconut shell carbon, soaking and stirring until no bubbles are generated, evaporating the solvent in a water bath at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, reducing with hydrogen at 300 ℃ for 2h to obtain activated carbon-loaded Pd/AC nano-particles, and then adding CO and C2H5Treating the mixed gas (the molar ratio is 10:1) of the I at 200 ℃ for 6.0h to obtain the P modified carbon-supported monatomic Pd catalyst, which is marked as follows: pd5an/AC-P catalyst. The prepared catalyst is an N-modified carbon-supported monatomic Pd catalyst which can be known by adopting X-ray diffraction XRD, X-ray absorption fine structure spectrum XAFS, spherical aberration electron microscope HAADF-STEM and the like.
Example 6
Pretreatment of a carbon carrier: the coconut shell activated carbon is treated by refluxing with sulfuric acid at 80 ℃ for 12h, and then dried at 120 ℃. 0.02g of PdCl is taken2Dissolving in 15ml deionized water, adding 10g of processed coconut shell carbon, soaking and stirring until no bubbles are generated, evaporating the solvent in a water bath at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, reducing with hydrogen at 300 ℃ for 2h to obtain activated carbon-loaded Pd/AC nano-particles, and then adding CO and C3H7Treating the mixed gas (molar ratio 50:1) of the catalyst I at 250 ℃ for 1.0h to obtain the S modified carbon-supported monatomic Pd catalyst, which is marked as: pd6an/AC-S catalyst. The prepared catalyst is an N-modified carbon-supported monatomic Pd catalyst which can be known by adopting X-ray diffraction XRD, an X-ray absorption fine structure spectrum XAFS, a spherical aberration electron microscope HAADF-STEM and the like.
Example 7
Pretreatment of a carbon carrier: dissolving thiourea in ether organic solvent, adding active coconut carbon, immersing and drying at 80 deg.C. 1.12g of PdCl are weighed out2Dissolving in 15ml deionized water, adding 10g coconut shell carbon, soaking and stirring until no bubble is generated, evaporating solvent in 90 deg.C water bath, oven drying at 120 deg.C for 8h, roasting at 300 deg.C under nitrogen protection for 4h, reducing with 300 deg.C hydrogen for 2h to obtain activated carbon-loaded Pd/AC nanoparticles, and adding CO and C6H5Treating the mixed gas I (the molar ratio is 100:1) at 150 ℃ for 0.1h to obtain the S modified carbon-supported monatomic Pd catalyst, which is marked as follows: pd6an/AC-S catalyst. The catalyst prepared by X-ray diffraction XRD, X-ray absorption fine structure spectrum XAFS, spherical aberration electron microscope HAADF-STEM and the like is an N-modified carbon-supported monatomic Pd catalyst.
Example 8
As a comparative example, the carbon support was taken without pretreatment and 1.12g of PdCl was measured2Dissolving in 15ml deionized water, adding 10g untreated coconut shell activated carbon, soaking and stirring until no bubbles are generated, evaporating the solvent in a water bath at 90 ℃, drying in an oven at 120 ℃ for 8h, roasting at 300 ℃ for 4h under the protection of nitrogen, reducing with hydrogen at 300 ℃ for 2h to obtain activated carbon-loaded Pd/AC nano-particles, and then adding CO and C6H5Treating the mixed gas (the molar ratio is 100:1) of the I at 200 ℃ for 0.1h to obtain the carbon-supported monatomic Pd catalyst without any modification, which is marked as follows: pd6an/AC catalyst. The catalyst prepared by X-ray diffraction XRD, X-ray absorption fine structure spectrum XAFS, spherical aberration electron microscope HAADF-STEM and the like is an N-modified carbon-supported monatomic Pd catalyst.
Acetylene is used as a reaction substrate, and the carbonylation reaction performance is tested.
300mg of each of the catalysts obtained in examples 1 to 8 was weighed and placed in a 25mL tank reactor containing 10g of methanol; introducing mixed gas containing air, CO and acetylene, reacting for 3 hours at the reaction temperature of 70 ℃ and the stirring speed of 600rpm, analyzing and calculating the conversion rate of acetylene and the selectivity of each product, and obtaining the results shown in Table 1.
Table 1 catalyst examples 1-7 application to carbonylation of acetylene to methyl ester
Figure BDA0002792870730000061
300mg of the catalyst obtained in example 1 was weighed and placed in a tank reactor containing 10g of the other alcohol in 25 mL; introducing mixed gas containing air, CO and acetylene C2H20.5MPa, CO 2.0MPa, and Air 3.0 MPa. The reaction temperature is 80 ℃, and the stirring speed is 600rpmAfter 3 hours of reaction, the acetylene conversion and the selectivity of each product were analyzed and calculated, and the results are detailed in table 2.
Table 2 catalyst example 1 Synthesis of various esters by carbonylation of acetylene
Figure BDA0002792870730000071
300mg of the catalyst obtained in example 1 was weighed and placed in a tank reactor containing 10g of methanol in 25 mL; introducing mixed gas containing Air (or not), CO, acetylene or other alkynes, wherein the alkynes are 0.01mol, the CO is 2.0MPa, and the Air is 3.0 MPa. After 3 hours of reaction at 80 ℃ and 600rpm stirring speed, acetylene conversion and selectivity of each product were analyzed and calculated, and the results are detailed in Table 3.
Table 3 catalyst example 1 for the carbonylation of various alkynes to synthesize esters
Figure BDA0002792870730000072
Figure BDA0002792870730000081
Data for reactions without air.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. The application of a carbon-supported monatomic Pd catalyst in alkyne dicarbonylation reaction; characterized in that the metal Pd in the catalyst is one of the ligand N, O, P, S which is monoatomic dispersed in the form of mononuclear complex containing carbonyl and iodine ligandsOne or more than two anchored carbon support surfaces; the content percentage of the metal in the carbon-based carrier is 0.1-5%, preferably 0.1-3%; under certain reaction conditions, C2nH2n、CO、O2And alcohol or water to produce olefin diacid and olefin diacid ester with two more carbons through active and high-selectivity double carbonylation reaction.
2. Use according to claim 1, characterized in that: pd in the catalyst is anchored on the oxygen, nitrogen, sulfur and phosphine functional group sites on the carrier in the form of a mononuclear complex of carbonyl halide, and the structural general formula can be represented as follows:
Pd(CO)xMy(O-C，N-C，S-C，P-C)
wherein: O-C, N-C, S-C, P-C respectively represents one or more than two of oxygen, nitrogen, sulfur and phosphine functional groups on the surface of the carbon carrier, x is 1 or 2, y is 1 or 2, and M is one or more than two of Cl, Br and I.
3. The use according to claim 1, wherein the carbon support is coconut shell activated carbon.
4. Use according to any one of claims 1 to 3, wherein the catalyst is prepared by: firstly, pretreating a carbon carrier to ensure that the surface of the carbon carrier is rich in N, O, P, S functional groups, then preparing carbon-supported Pd nano metal particles by a method of impregnation, roasting and reduction, and then carrying out monodispersion heat treatment by utilizing CO and halogen, halogen acid or halogenated hydrocarbon to prepare the carbon-supported carbonyl-and halogen-containing coordinated Pd mononuclear complex catalyst.
5. Use according to claim 4, characterized in that:
pretreating a carbon carrier to enable the carbon carrier to contain one or more than two coordination groups of N, O, P, S and the like for anchoring a mononuclear complex containing carbonyl or halogen coordination Pd; the specific process is that N-containing group adopts NH3Introducing a flow tube filled with carbon carriers for 500-900 ℃ treatmentDissolving porphyrin compounds in a corresponding solvent, soaking a carbon carrier, removing the solvent at 60-80 ℃, and treating for 2-12 hours at 300-500 ℃; carrying out oxidation treatment on the O-containing group in a kettle for 2-6 h at the temperature of 200-400 ℃ by using nitric acid; the P-containing group being PCl3Introducing saturated steam at 60-80 ℃ into a flowing pipe with a carbon carrier for treatment at 500-900 ℃ for 2-12 h, or dissolving vinyl triphenylphosphine monomer in tetrahydrofuran, adding an azodiisobutyronitrile initiator for polymerization, adding the carbon carrier for impregnation, drying at 60-80 ℃, drying again at 100-120 ℃, and treating again at 300-350 ℃; and carrying out reflux treatment on the carbon carrier by adopting S-containing groups at the temperature of 80-100 ℃ by adopting sulfuric acid, or dissolving thiourea and the like in an ether organic solvent, and then adding the carbon carrier for dipping treatment.
The pretreated carbon carrier is loaded with Pd metal by dipping, roasting and H2Is prepared after reduction.
6. Use according to claim 4, characterized in that: the halogen, halogen acid or halogenated alkane used includes Cl2、Br2、I2Etc. halogen, or HCl, HBr, HI or CH3Cl、CH3Br、CH3CH2Br、CH3CH2CH2Br、CH3I、CH3CH2I、CH3CH2CH2I. One or more than two of iodobenzene; preferably one or more of bromine, iodine, bromide or iodide, and more preferably one or two of iodine or iodide; the halogen, halogen acid or halogenated alkane can be introduced into the reaction system by CO bubbling or by a pump.
7. Use according to claim 4, characterized in that: the conditions of the monodisperse heat treatment are that the temperature is 100-350 ℃, the pressure is 0.1-3.0 MPa, the molar ratio of CO to (one or more than two of halogen, halogen acid or halogenated hydrocarbon) is 0.1-10, and the treatment time is 10 min-10 h.
8. The method of claim 1, wherein the raw materials are alkyne, water or alcohol, CO, O2The reaction conditions are 40-150 ℃, and CO and O are2The partial pressure of the reaction is 0.1-5.0 MPa, the mol ratio of alkyne to water or alcohol is 1 (2-10), the mol ratio of alkyne to CO is 1 (1-30), and CO and O are respectively2The molar ratio of (1) to (5).
9. The use according to claim 8,
the alkyne comprises one or more of acetylene, propine, butyne, pentyne, hexyne, heptyne, octyne, phenylacetylene and the like; the alcohol is one of methanol, ethanol, propanol, butanol, pentanol and octanol.
10. The use of claim 1, 8 or 9, wherein the reaction is carried out in a tank reactor, and the molar ratio of the reaction substrate alkyne to Pd in the catalyst is 2000-15000.
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