CN114524729B - Application of carbon-supported monoatomic Pd catalyst in alkyne carbonylation reaction - Google Patents

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

Info

Publication number
CN114524729B
CN114524729B CN202011320908.2A CN202011320908A CN114524729B CN 114524729 B CN114524729 B CN 114524729B CN 202011320908 A CN202011320908 A CN 202011320908A CN 114524729 B CN114524729 B CN 114524729B
Authority
CN
China
Prior art keywords
carbon
catalyst
carbon carrier
reaction
halogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011320908.2A
Other languages
Chinese (zh)
Other versions
CN114524729A (en
Inventor
冯四全
丁云杰
宋宪根
李星局
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN202011320908.2A priority Critical patent/CN114524729B/en
Priority to PCT/CN2021/099116 priority patent/WO2022105199A1/en
Publication of CN114524729A publication Critical patent/CN114524729A/en
Application granted granted Critical
Publication of CN114524729B publication Critical patent/CN114524729B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/40—Succinic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/60—Maleic acid esters; Fumaric acid esters

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The application of a carbon-supported monoatomic Pd catalyst in alkyne dicarbonylation reaction. Wherein Pd in the catalyst is monoatomically anchored on the surface of the carbon carrier containing the ligand group N, O, P, S in the form of a mononuclear complex of carbonyl iodide. Under certain reaction conditions, C 2nH2n、CO、O2 and alcohol ROH or water H 2 O can be subjected to active and high-selectivity double-carbonylation reaction to generate olefin diacid and olefin diacid ester with more than two carbons. The catalyst is applied to alkyne dicarbonylation reaction, and has good catalytic activity and stability.

Description

Application of carbon-supported monoatomic Pd catalyst in alkyne carbonylation reaction
Technical Field
The invention belongs to the technical field of catalytic chemical industry, and particularly relates to application of a carbon-supported single-atom Pd catalyst in alkyne carbonylation reaction.
Background
In industrial catalysts, the supported metal catalyst accounts for more than 70%, and particularly the supported noble metal catalyst is widely used for various catalyst reactions. In actual industrial production, the supported metal catalyst is usually a nano metal catalyst, and only atoms with exposed surfaces often have catalyst activity, so that the utilization efficiency of metal atoms is low, and noble metal resources are wasted.
Compared with nano-metal catalysts, single-atom catalysts are emerging hot spots for contemporary research due to their nearly 100% atomic utilization, as well as single catalytically active sites.
The carbon-supported monoatomic Pd catalyst can be prepared by carrying out monodisperse heat treatment on the supported nano metal particles by using CO and CH 3 I, and carrying out in-situ atomic-level monodispersion on.
Acetylene, molecular formula C 2H2, commonly known as carbide gas, is an important organic synthesis raw material, called "industrial mother of organic synthesis". The calcium carbide can be easily prepared by adding water, and the calcium carbide in Xinjiang areas of China is rich and can be produced in a large amount. Other alkynes can be selectively prepared by utilizing acetylene, so that the scale of alkynes and the utilization of upstream and downstream products are enriched.
Taking acetylene as an example, under certain conditions, the acetylene is polymerized to generate aromatic hydrocarbons such as benzene, toluene, dimethylbenzene, naphthalene, anthracene, styrene, indene and the like. By substitution and addition reactions, a range of extremely valuable products can be produced. For example, acetylene dimerizes to vinyl acetylene, and the vinyl acetylene is further subjected to addition reaction with hydrogen chloride to obtain chloroprene; preparing acetaldehyde by directly hydrating acetylene; adding acetylene and hydrogen chloride to prepare chloroethylene; reacting acetylene with acetic acid to obtain vinyl acetate; reacting acetylene with hydrogen cyanide to prepare acrylonitrile; reacting acetylene with ammonia to produce picoline and 2-methyl-5-ethylpyridine; the acetylene reacts with toluene to form xylyl ethylene, which is further cracked by a catalyst to form three isomers of methylstyrene: acetylene is condensed with one molecule of formaldehyde to obtain propynyl alcohol, and is condensed with two molecules of formaldehyde to obtain butynyl glycol; methyl alkynol can be prepared by the addition reaction of acetylene and acetone, and isoprene is generated by the reaction; the acrylic acid and the derivatives thereof are prepared by the reaction of acetylene, carbon monoxide, other compounds (such as water, alcohol, mercaptan) and the like.
In addition, the downstream fine chemicals of acetylene are one direction of the chemical development of acetylene and other alkynes, and can promote the development of modern acetylene chemical products to the depth direction. Alkyne carbonylation reactions can occur with the evolution of nucleophiles using alkynes and CO as raw materials.
Among them, the carbonylation of acetylene to acrylic acid and esters is a typical example of industrial applications. However, most of these studies are homogeneous catalysis, and the focus of the studies is mainly focused on the field of catalysts, and [ Ni (CO) 4],[Co(CO)4]2,Fe(CO)5 and Pd catalytic systems are developed, which are mainly used for homogeneous catalysis reaction to prepare acrylic acid and acrylic acid esters. Pd catalytic system is used to introduce nitrogen-oxygen ligand, and the selectivity of the product can be regulated under the action of concentrated sulfuric acid, sulfonic acid and the like, so as to produce the products such as butenedioic acid ester, succinic acid ester, maleic anhydride and the like.
In summary, the existing acetylenic carbonylation has the following problems: (1) The catalyst is easy to run off, and the product is difficult to separate; (2) Taking acetylene as an example, most of the products are acrylic acid and acrylic ester, and other alkynes have less research and development; and (3) the catalyst dosage is large and the efficiency is low. The few supported metal catalysts are also metal nano metal catalysts, and the metal atom utilization rate is low.
Disclosure of Invention
The technical scheme of the invention is as follows: the N, O, P, S modified carbon-supported monoatomic Pd catalyst and the application thereof in the dicarbonylation reaction 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%, and the catalyst has higher technical competitive advantage. Under certain reaction conditions and the
The specific scheme is the application of the carbon-supported monoatomic Pd catalyst in alkyne dicarbonylation reaction; wherein the metal Pd in the catalyst is monoatomically dispersed on the surface of one or more than two anchored carbon carriers containing ligand N, O, P, S in the form of mononuclear complex containing carbonyl and iodine ligands. The content percentage of the metal mass in the carbon-based carrier is 0.1-5%, and the preferable content percentage is 0.1-3%; under certain reaction conditions, C 2nH2n、CO、O2 and alcohol or water can be subjected to active and high-selectivity dicarbonylation reaction to generate olefin diacid and olefin diacid ester with two more carbons.
Pd in the catalyst is anchored on oxygen, nitrogen, sulfur and phosphine functional groups sites on a carrier in the form of mononuclear complex of carbonyl halide, and the structural general formula can be expressed as:
Pd(CO)x M y(O-C，N-C，S-C，P-C)
Wherein: O-C, N-C, S-C, P-C is respectively represented by one or more than two of oxygen, nitrogen, sulfur and phosphine functional groups on the surface of a 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: pretreating a carbon carrier to enable the surface of the carbon carrier to be rich in N, O, P, S functional groups, preparing carbon-supported Pd nano metal particles by means of impregnation, roasting and reduction, and then carrying out monodisperse heat treatment on CO and halogen, halogen acid or halogenated hydrocarbon to obtain the carbon-supported Pd mononuclear complex catalyst containing carbonyl and halogen coordination.
The carbon support is subjected to pretreatment such that the carbon support contains one or more of N, O, P, S or other coordinating groups for anchoring the mononuclear complex containing the carbonyl group or the halogen-coordinated Pd. The specific process is as follows: introducing NH 3 into a flow pipe filled with a carbon carrier for 2-12 h at 500-900 ℃ or dissolving porphyrin compounds in a corresponding solvent for soaking the carbon carrier, removing the solvent at 60-80 ℃ and then treating for 2-12 h at 300-500 ℃; oxidizing the O-containing group in a small kettle at 200-400 ℃ for 2-6 h by adopting nitric acid; the P-containing group is substituted into a flow pipe filled with a carbon carrier by saturated steam at 60-80 ℃ through PCl 3 for 2-12 hours at 500-900 ℃, or vinyl triphenylphosphine monomer is dissolved in tetrahydrofuran, azo diisobutyronitrile initiator is added for polymerization, then the carbon carrier is added for impregnation, then the carbon carrier is dried at 60-80 ℃, then the carbon carrier is dried again at 100-120 ℃ for further treatment at 300-350 ℃; the S-containing group is treated by reflux treatment of the carbon carrier by sulfuric acid at 80-100 ℃, or is treated by dipping the carbon carrier by dissolving thiourea and the like in an ether organic solvent.
The Pd metal loading process of the pretreated carbon carrier is prepared by impregnating, roasting and reducing H 2 of a precursor of Pd metal.
Halogen, halogen acid or halogenated alkane used comprises one or more than two of halogen such as Cl 2、Br2、I2, or HCl, HBr, HI or CH3Cl、CH3Br、CH3CH2Br、CH3CH2CH2Br、CH3I、CH3CH2I、CH3CH2CH2I、 iodobenzene; preferably one or more of bromine, iodine, bromide or iodide, further preferably one or more of iodine or iodide; the halogen, halogen acid or halogenated alkane can be introduced into the reaction system through CO bubbling or through a pump.
The condition of the monodisperse heat treatment is that the temperature is 100-350 ℃, the pressure is 0.1-3.0 MPa, the mole 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 O 2, the reaction conditions are 40-150 ℃, the partial pressures of CO and O 2 are respectively 0.1-5.0 MPa, in the reaction, the molar ratio of alkyne to water or alcohol is 1 (2-10), the molar ratio of alkyne to CO is 1 (1-30), and the molar ratio of CO to O 2 is 1 (1-5).
The use according to claim 8, wherein,
The alkyne comprises one or more than two of acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne, phenylacetylene and the like; the alcohol is one of methanol, ethanol, propanol, butanol, amyl alcohol and octanol.
The reaction is carried out in a kettle type reactor, and the molar ratio of alkyne as a reaction substrate to Pd in the catalyst is 2000-15000.
Under the carbon-supported monoatomic 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 substrate comprises acetylene, CO, water and acetic acid, wherein the acetic acid is a solvent; when preparing propionate, the composition of the reaction substrate is acetylene, CO and corresponding alcohol; when the butenedioic acid is prepared, the reaction components are acetylene, CO, air, water and acetic acid, wherein the acetic acid is a solvent; in the preparation of butenedioic acid esters, the reaction components are acetylene, CO, air and the corresponding alcohols. Other alkynes are similar.
The beneficial effects of the application include, but are not limited to:
compared with the prior art, the invention provides a N, O, P, S modified carbon-supported monoatomic Pd catalyst and application thereof in alkyne dicarbonylation reaction. The catalyst Pd used in the method is a supported single-metal active site Pd catalyst, and belongs to the category of single-atom catalysis. Pd is atomically dispersed on the surface of a carrier modified by N, O, P, S functional groups in the form of a mononuclear complex of palladium carbonyl iodide, and is applied to carbonylation reactions of acetylene and the like, the process is novel and simple, the condition is mild, the reaction activity is good, the product selectivity is high, corrosive sulfuric acid, hydrochloric acid and other solvents are not required to be added in the reaction process, and cocatalysts such as sulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like are not required to be added in the reaction process, so that the corrosion of equipment is avoided, the innovation is strong, and the method has higher technical competitive advantage.
Drawings
FIG. 1 is a transmission electron micrograph of sample Pd 1/AC.
FIG. 2 is a ball-point-differential electron microscope photograph of sample Pd 1/AC.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and reagents used in the application are all commercially purchased and are directly used without treatment, and the instruments and equipment used adopt the schemes and parameters recommended by manufacturers.
In an example, the transmission electron microscope was used for detection by an instrument of JEM-2100, japan.
In the examples, the spherical aberration is detected by an instrument of JEM-ARM 200F.
In the examples, all catalyst evaluation results adopt Agilent 7890B type liquid chromatograph, FID detector, capillary column, internal standard method analysis of liquid phase composition, methyl benzoate as internal standard;
and calculating according to the composition of each product to obtain the product selectivity.
In the examples of the present application, the conversion of acetylene and the selectivity of the product were calculated based on the number of moles of carbon in the converted acetylene.
Example 1
Pretreatment of a carbon carrier: NH 3 was introduced into a flow tube containing coconut activated carbon and treated at 800℃for 6h. Weighing 0.17g of PdCl 2, dissolving in 15ml of deionized water, adding 10g of treated coconut shell activated carbon, immersing, stirring until no bubble is generated, evaporating a solvent in a water bath at 90 ℃, drying in a baking oven at 120 ℃ for 8 hours, roasting at 300 ℃ under nitrogen protection for 4 hours, reducing with hydrogen at 300 ℃ for 2 hours to obtain activated carbon-supported Pd/AC nano-particles, and treating with a mixed gas of CO and CH 3 I (molar ratio of 1:1) at 100 ℃ for 0.5 hour to obtain the N-modified carbon-supported single-atom Pd catalyst, wherein the N-modified carbon-supported single-atom Pd catalyst is marked as follows: pd 1/AC-N catalyst. The catalyst prepared by adopting X-ray diffraction XRD, X-ray absorption fine structure spectrum XAFS, a spherical aberration electron microscope HAADF-STEM and the like is known to be an N-modified carbon-supported monoatomic Pd catalyst.
Example 2
Pretreating a carbon carrier, namely dissolving porphyrin in ethyl acetate, soaking coconut shell activated carbon, removing a solvent at 60-80 ℃ and treating for 6 hours at 350 ℃; weighing 0.51g of PdCl 2, dissolving in 15ml of deionized water, adding 10g of treated coconut shell carbon, immersing, stirring until no bubble is generated, evaporating a solvent in a water bath at 90 ℃, drying in a baking oven at 120 ℃ for 8 hours, roasting at 300 ℃ under nitrogen protection for 4 hours, reducing with hydrogen at 300 ℃ for 2 hours to obtain activated carbon-supported Pd/AC nano-particles, and treating with a mixed gas of CO and CH 2I2 (molar ratio of 0.5:1) at 250 ℃ for 0.5 hour to obtain the N-modified carbon-supported single-atom Pd catalyst, wherein the N-modified carbon-supported single-atom Pd catalyst is marked as follows: pd 2/AC-N catalyst. The prepared catalyst is known to be an N-modified carbon-supported monoatomic Pd catalyst by adopting X-ray diffraction XRD, 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 at 200-400 ℃ into a small pot, adding coconut shell activated carbon for oxidation treatment for 6h, and drying at 120 ℃. Measuring 0.22g Pd (NO 3)2 is dissolved in 15ml deionized water, then 10g treated coconut shell carbon is added, dipping and stirring are carried out until NO bubble is generated, then the solvent is evaporated in a water bath at 90 ℃, the solvent is dried in a baking oven at 120 ℃ for 8 hours, the catalyst is baked for 4 hours under the protection of nitrogen at 300 ℃, then the activated carbon-loaded Pd/AC nano-particles are obtained after reduction for 2 hours by hydrogen at 300 ℃, then the mixed gas of CO and CH 3 Br (molar ratio 1:1) is treated for 2.0 hours at 200 ℃, thus obtaining the O-modified carbon-loaded monoatomic Pd catalyst, which is marked as Pd 3/AC-O catalyst.
Example 4
Pretreatment of carbon carriers: PCl 3 was introduced into a flow tube containing coconut shell activated carbon at 80deg.C with saturated steam and treated at 650deg.C for 12h. Weighing 0.18g of Pd (OAc) 2, dissolving in 15ml of deionized water, adding 10g of treated coconut shell carbon, immersing, stirring until no bubble is generated, evaporating a solvent in a water bath at 90 ℃, drying in a baking oven at 120 ℃ for 8 hours, roasting at 300 ℃ under nitrogen protection for 4 hours, reducing with hydrogen at 300 ℃ for 2 hours to obtain activated carbon-supported Pd/AC nano-particles, and treating with a mixed gas (molar ratio of CO to C 2H5 Br is 5:1) at 150 ℃ for 3.0 hours to obtain the P modified carbon-supported single-atom Pd catalyst, wherein the P modified carbon-supported single-atom Pd catalyst is marked as follows: pd 4/AC-P catalyst. The prepared catalyst is known to be an N-modified carbon-supported monoatomic Pd catalyst by adopting X-ray diffraction XRD, X-ray absorption fine structure spectrum XAFS, a spherical aberration electron microscope HAADF-STEM and the like.
Example 5
Pretreatment of carbon carriers: dissolving vinyl triphenylphosphine monomer in tetrahydrofuran, adding azodiisobutyronitrile initiator for polymerization, adding coconut activated carbon for impregnation, drying at 60-80 ℃, drying at 120 ℃ again, and treating again under the protection of He at 300 ℃. Weighing 0.85g of PdCl 2, dissolving in 15ml of deionized water, adding 10g of treated coconut shell carbon, immersing and stirring until no bubble is generated, evaporating a solvent in a water bath at 90 ℃, drying in a baking oven at 120 ℃ for 8 hours, roasting at 300 ℃ under nitrogen protection for 4 hours, reducing with hydrogen at 300 ℃ for 2 hours to obtain activated carbon-supported Pd/AC nano-particles, and treating with a mixed gas of CO and C 2H5 I (molar ratio of 10:1) at 200 ℃ for 6.0 hours to obtain the P modified carbon-supported single-atom Pd catalyst, wherein the P modified carbon-supported single-atom Pd catalyst is marked as follows: pd 5/AC-P catalyst. The prepared catalyst is known to be an N-modified carbon-supported monoatomic Pd catalyst by adopting X-ray diffraction XRD, X-ray absorption fine structure spectrum XAFS, a spherical aberration electron microscope HAADF-STEM and the like.
Example 6
Pretreatment of a carbon carrier: and (3) carrying out reflux treatment on the coconut shell activated carbon at the temperature of 80 ℃ by using sulfuric acid for 12 hours, and drying at the temperature of 120 ℃. Dissolving 0.02g of PdCl 2 in 15ml of deionized water, adding 10g of treated coconut shell carbon, immersing and stirring until no bubble is generated, evaporating a solvent in a water bath at 90 ℃, drying in a baking oven at 120 ℃ for 8 hours, roasting at 300 ℃ under nitrogen protection for 4 hours, reducing with hydrogen at 300 ℃ for 2 hours to obtain activated carbon-supported Pd/AC nano particles, and treating with a mixed gas of CO and C 3H7 I (molar ratio of 50:1) at 250 ℃ for 1.0 hour to obtain the S-modified carbon-supported single-atom Pd catalyst, wherein the S-modified carbon-supported single-atom Pd catalyst is marked as follows: pd 6/AC-S catalyst. The prepared catalyst is known to be an N-modified carbon-supported monoatomic Pd catalyst by adopting X-ray diffraction XRD, X-ray absorption fine structure spectrum XAFS, a spherical aberration electron microscope HAADF-STEM and the like.
Example 7
Pretreatment of carbon carriers: dissolving thiourea and the like in an diethyl ether organic solvent, then adding coconut shell active carbon for soaking, and drying at 80 ℃. 1.12g of PdCl 2 is measured and dissolved in 15ml of deionized water, 10g of coconut charcoal is added, after dipping and stirring until no bubble is generated, the solvent is evaporated in a water bath at 90 ℃, the solvent is dried in a baking oven at 120 ℃ for 8 hours, the Pd/AC nano-particles loaded by activated carbon are obtained after nitrogen protection roasting at 300 ℃ for 4 hours, then the Pd/AC nano-particles loaded by activated carbon are obtained after hydrogen reduction at 300 ℃ for 2 hours, and then the Pd/AC nano-particles are treated for 0.1 hour at 150 ℃ by using a mixed gas (the molar ratio of CO to C 6H5 I is 100:1), so that the S modified carbon-loaded single-atom Pd catalyst is obtained, and the S modified carbon-loaded single-atom Pd catalyst is marked as follows: pd 6/AC-S catalyst. The catalyst prepared by adopting X-ray diffraction XRD, X-ray absorption fine structure spectrum XAFS, a spherical aberration electron microscope HAADF-STEM and the like is known to be an N-modified carbon-supported monoatomic Pd catalyst.
Example 8
As a comparison example, 1.12g of PdCl 2 is measured to be dissolved in 15ml of deionized water without pretreatment, 10g of untreated coconut shell activated carbon is added, after soaking and stirring until no bubble is generated, the solvent is evaporated in a water bath at 90 ℃, the solvent is dried in an oven at 120 ℃ for 8 hours, the Pd/AC nano particles loaded by the activated carbon are obtained after nitrogen protection roasting at 300 ℃ and hydrogen reduction at 300 ℃ for 2 hours, and then the Pd/AC nano particles loaded by the activated carbon are obtained after treatment for 0.1 hour at 200 ℃ by using a mixed gas (molar ratio of 100:1) of CO and C 6H5 I, and the carbon-loaded single-atom Pd catalyst without any modification is obtained, and the catalyst is marked as follows: pd 6/AC catalyst. The catalyst prepared by adopting X-ray diffraction XRD, X-ray absorption fine structure spectrum XAFS, a spherical aberration electron microscope HAADF-STEM and the like is known to be an N-modified carbon-supported monoatomic Pd catalyst.
Acetylene is used as a reaction substrate, and the carbonylation reaction performance is tested.
300Mg of the catalyst obtained in examples 1 to 8 were weighed out respectively and placed in a 25mL tank reactor containing 10g of methanol; introducing a mixed gas containing air, CO and acetylene, reacting at 70 ℃ and a stirring speed of 600rpm for 3 hours, and analyzing and calculating the conversion rate of acetylene and the selectivity of each product, wherein the results are shown in Table 1.
Table 1 catalyst examples 1-7 apply to the carbonylation of acetylene to methyl esters
300Mg of the catalyst obtained in example 1 were weighed and placed in a kettle reactor containing 10g of other alcohols in 25 mL; introducing a mixed gas containing air, CO and acetylene, wherein the pressure of the mixed gas is 0.5MPa, the pressure of the CO is 2.0MPa, and the pressure of the air is 3.0MPa. After 3 hours of reaction at 80℃and 600rpm stirring speed, the conversion of acetylene and the selectivity of each product were analyzed and calculated, and the results are shown in Table 2.
Table 2 catalyst example 1 for the carbonylation of acetylene to various esters
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, CO is 2.0MPa, and air is 3.0 MPa. After 3 hours of reaction at 80℃and 600rpm stirring speed, the conversion of acetylene and the selectivity of each product were analyzed and calculated, and the results are shown in Table 3.
Table 3 catalyst example 1 for the carbonylation of various alkynes to esters
* Is the reaction data without air.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.

Claims (7)

1. Application of carbon-supported monoatomic Pd catalyst in alkyne dicarbonylation reaction; wherein the metal Pd in the catalyst is monoatomically dispersed on the surface of one or more than two anchored carbon carriers containing ligand N, O, P, S in the form of mononuclear complex containing carbonyl and iodine ligands; the content percentage of the metal mass in the carbon-based carrier is 0.1-5%; the reaction conditions are as follows: performing a dicarbonylation reaction at 40-150 ℃ under the conditions that partial pressures of CO and O 2 are respectively 0.1-5.0 MPa and alkyne, CO, O 2 and alcohol or water exist to generate alkene diacid ester with more two carbons;
pd in the catalyst is anchored on oxygen, nitrogen, sulfur and phosphine functional groups sites on a carrier in the form of mononuclear complex of carbonyl halide, and the structural general formula is shown as follows:
Pd(CO)x M y(O-C，N-C，S-C，P-C)
Wherein: O-C, N-C, S-C, P-C is respectively represented as oxygen, nitrogen, sulfur and phosphine functional groups on the surface of a carbon carrier, x is 1 or 2, y is 1 or 2, M is one or more than two of Cl, br and I, alkyne is one or more than two of acetylene, propyne, butyne, pentyne, hexyne, heptyne, octyne and phenylacetylene,
The preparation process of the catalyst comprises the following steps: pretreating a carbon carrier to enable the surface of the carbon carrier to be rich in N, O, P, S functional groups, preparing carbon-supported Pd nano metal particles by a dipping, roasting and reducing method, and then carrying out monodisperse heat treatment on CO and halogen, halogen acid or halogenated hydrocarbon to obtain the carbon-supported Pd mononuclear complex catalyst containing carbonyl and halogen coordination;
Pretreatment of a carbon carrier, wherein the carbon carrier contains one or more than two of N, O, P, S coordination groups for anchoring mononuclear complexes containing carbonyl or halogen coordination Pd; the specific process comprises the steps of introducing NH 3 into a flow pipe filled with a carbon carrier for 2-12 hours at 500-900 ℃ or dissolving porphyrin in a corresponding solvent, then immersing the carbon carrier, removing the solvent at 60-80 ℃ and then treating for 2-12 hours at 300-500 ℃; oxidizing the O-containing group in a small kettle at 200-400 ℃ for 2-6 h by adopting nitric acid; the P-containing group is substituted into a flow tube filled with a carbon carrier by adopting PCl 3 at the temperature of 60-80 ℃ and saturated steam for 2-12 hours at the temperature of 500-900 ℃, or vinyl triphenylphosphine monomer is dissolved in tetrahydrofuran, azo diisobutyronitrile initiator is added for polymerization, then the carbon carrier is added for soaking, then the carbon carrier is dried at the temperature of 60-80 ℃, then the carbon carrier is dried again at the temperature of 100-120 ℃ and the carbon carrier is treated again at the temperature of 300-350 ℃; reflux treatment is carried out on the carbon carrier by adopting sulfuric acid at 80-100 ℃, or thiourea is adopted to dissolve in an ether organic solvent, and then the carbon carrier is added for impregnation treatment;
The Pd metal is loaded on the pretreated carbon carrier, and the Pd metal is prepared by impregnating, roasting and reducing H 2 of a precursor of the Pd metal;
Halogen, halogen acid or halogenated hydrocarbon, wherein the halogen is Cl 2、Br2 or I 2, the halogen acid is HCl, HBr or HI, and the halogenated hydrocarbon is one or more than two of CH3Cl、CH3Br、CH3CH2Br、CH3CH2CH2Br、CH3I、CH3CH2I、CH3CH2CH2I or iodobenzene; the halogen, halogen acid or halohydrocarbon is introduced into the reaction system by CO bubbling, or introduced into the reaction system by a pump.
2. The use according to claim 1, wherein the carbon carrier is coconut activated carbon.
3. Use according to claim 1, characterized in that the percentage of metal mass in the carbon-based support is 0.1-3%.
4. The use according to claim 1, characterized in that: the condition of the monodisperse heat treatment is that the temperature is 100-350 ℃, the pressure is 0.1-3.0 MPa, the mole 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.
5. The application of claim 1, wherein the reaction raw materials are alkyne, water or alcohol, CO and O 2, the molar ratio of alkyne to water or alcohol is 1:2-10, the molar ratio of alkyne to CO is 1:1-30, and the molar ratio of CO to O 2 is 1:1-5.
6. The use according to claim 5, wherein,
The alcohol is one of methanol, ethanol, propanol, butanol, amyl alcohol and octanol.
7. The use according to claim 1, 5 or 6, characterized in that the reaction is carried out in a tank reactor with a molar ratio of the reaction substrate alkyne to Pd in the catalyst of 2000-15000.
CN202011320908.2A 2020-11-23 2020-11-23 Application of carbon-supported monoatomic Pd catalyst in alkyne carbonylation reaction Active CN114524729B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202011320908.2A CN114524729B (en) 2020-11-23 2020-11-23 Application of carbon-supported monoatomic Pd catalyst in alkyne carbonylation reaction
PCT/CN2021/099116 WO2022105199A1 (en) 2020-11-23 2021-06-09 Palladium-based catalyst, preparation method therefor and use thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011320908.2A CN114524729B (en) 2020-11-23 2020-11-23 Application of carbon-supported monoatomic Pd catalyst in alkyne carbonylation reaction

Publications (2)

Publication Number Publication Date
CN114524729A CN114524729A (en) 2022-05-24
CN114524729B true CN114524729B (en) 2024-06-11

Family

ID=81619383

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011320908.2A Active CN114524729B (en) 2020-11-23 2020-11-23 Application of carbon-supported monoatomic Pd catalyst in alkyne carbonylation reaction

Country Status (2)

Country Link
CN (1) CN114524729B (en)
WO (1) WO2022105199A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114539056B (en) * 2020-11-24 2023-03-14 中国科学院大连化学物理研究所 Method for preparing methyl acetate by methanol carbonylation
CN115888786A (en) * 2022-10-26 2023-04-04 鄂尔多斯市瀚博科技有限公司 Si-modified acetylene hydrochlorination metal-free catalyst, preparation method and application

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109126774A (en) * 2017-06-15 2019-01-04 中国科学院大连化学物理研究所 A kind of monatomic noble metal catalyst of super high-dispersion loading type and preparation method thereof
CN110560086A (en) * 2019-08-30 2019-12-13 浙江工业大学 High-dispersion palladium-sulfur-doped active carbon catalyst and preparation and application thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105753700B (en) * 2014-12-19 2018-06-08 中国科学院大连化学物理研究所 A kind of method of acetylene carbonylation synthesizing methyl acrylate
CN106854159B (en) * 2015-12-09 2019-01-04 中国科学院大连化学物理研究所 A kind of phenylacetylene carbonyl compound at unsaturated aromatic ester method
JP6871802B2 (en) * 2016-07-28 2021-05-12 エヌ・イーケムキャット株式会社 A method for obtaining a carbonyl compound by a carbonylation reaction of a halogen compound using an aldehyde as a carbon monoxide source in the presence of a heterogeneous palladium catalyst.
CN107739309B (en) * 2017-10-30 2020-08-28 中国成达工程有限公司 Double-carbonylation preparation method of palladium-catalyzed acetylene
CN111195516B (en) * 2018-11-20 2021-04-23 中国科学院大连化学物理研究所 Atomic-level monodisperse rhodium-based catalyst, preparation method thereof and application of atomic-level monodisperse rhodium-based catalyst in preparation of methyl acetate through methanol gas-phase carbonylation
CN111195530B (en) * 2018-11-20 2021-04-23 中国科学院大连化学物理研究所 Atomic-level monodisperse iridium-based catalyst and preparation method and application thereof
CN111195529B (en) * 2018-11-20 2021-05-25 中国科学院大连化学物理研究所 Rhodium-based catalyst, preparation method thereof and application thereof in methanol gas-phase carbonylation reaction
CN111195515B (en) * 2018-11-20 2021-04-23 中国科学院大连化学物理研究所 Monoatomic dispersion noble metal catalyst, preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109126774A (en) * 2017-06-15 2019-01-04 中国科学院大连化学物理研究所 A kind of monatomic noble metal catalyst of super high-dispersion loading type and preparation method thereof
CN110560086A (en) * 2019-08-30 2019-12-13 浙江工业大学 High-dispersion palladium-sulfur-doped active carbon catalyst and preparation and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"The highly efficient and selective dicarbonylation of acetylene catalysed by palladium nanosheets supported on activated carbon";Xuemei Wei等;《New J. Chem.》;第44卷;第11835-11840页 *

Also Published As

Publication number Publication date
WO2022105199A1 (en) 2022-05-27
CN114524729A (en) 2022-05-24

Similar Documents

Publication Publication Date Title
CN114524729B (en) Application of carbon-supported monoatomic Pd catalyst in alkyne carbonylation reaction
CN102847550B (en) Catalyst for preparation of acetic acid and methyl acetate through carbonylation of methanol and preparation method thereof
CN104959154B (en) A kind of method for preparing the catalyst of levulinate and levulinate being prepared with it
Chen et al. Xylan-type hemicellulose supported palladium nanoparticles: a highly efficient and reusable catalyst for the carbon–carbon coupling reactions
Berenblyum et al. Supported palladium nanomaterials as catalysts for petroleum chemistry: 2. Kinetics and specific features of the mechanism of selective hydrogenation of phenylacetylene in the presence of carbon-supported palladium nanocatalyst
Jiang et al. Effect of different synthetic routes on the performance of propylene hydroformylation over 3V-PPh 3 polymer supported Rh catalysts
CN104107718B (en) Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof
CN106866589A (en) A kind of preparation method of γ valerolactones
CN110614093A (en) Preparation method of low-content gold and ruthenium bimetallic catalyst for acetylene hydrochlorination
Arai Hydroformylation, hydrogenation, and isomerization of olefins over polymer-immobilized rhodium complexes
CN111195514B (en) Monoatomic dispersion rhodium-based catalyst, preparation method thereof and application thereof in methane low-temperature oxidation reaction
CN109438153B (en) Method for preparing 2, 6-dimethyl-2-heptene through citronellal selective decarbonylation reaction
CN105056969A (en) Preparation method of low-precious metal Au-Cu-TiO2/C catalyst for acetylene hydrochlorination reaction
CN105727991A (en) Pd-Cu-series supported hydrogenation catalyst
CN105727990A (en) Preparation method of Pd-Cu-series supported hydrogenation catalyst
CN106552657A (en) A kind of platinum based catalyst of SiC carriers confinement and preparation method thereof
CN114797929A (en) Porous nitrogen modified carbon material loaded cobalt-based catalyst and preparation and application thereof
CN114524719A (en) Method for preparing acetaldehyde, ethanol and ethyl acetate by methanol reduction carbonylation
CN105727992A (en) Pd-Ni-series supported hydrogenation catalyst
Li et al. Nickel–copper catalysts supported by boron and nitrogen co-doped activated carbon for gas phase carbonylation of ethanol
CN114522683B (en) Carbon-supported Pd-M bimetallic single-atom catalyst and application thereof in C2H2Application in double carbonylation reaction
Mirzoeva et al. Catalytic hydrogenation properties of Pd-and Rh-containing polymers immobilized on Al2O3
CN114539056B (en) Method for preparing methyl acetate by methanol carbonylation
Tao et al. Microporous nitrogen-doped carbon from polyaniline as a highly efficient and stable catalyst for acetylene hydrochlorination
CN116532155A (en) Pd-based bimetallic catalyst loaded by quaternary phosphonium salt ionic polymer, and preparation and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant