CN114515604A - Quaternary phosphonium salt polymer loaded bimetallic monatomic catalyst, preparation method and application - Google Patents

Quaternary phosphonium salt polymer loaded bimetallic monatomic catalyst, preparation method and application Download PDF

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CN114515604A
CN114515604A CN202011456302.1A CN202011456302A CN114515604A CN 114515604 A CN114515604 A CN 114515604A CN 202011456302 A CN202011456302 A CN 202011456302A CN 114515604 A CN114515604 A CN 114515604A
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phosphonium salt
quaternary phosphonium
salt polymer
complex
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丁云杰
宋宪根
李彬
冯四全
姜淼
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Dalian Institute of Chemical Physics of CAS
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Abstract

The application discloses a quaternary phosphonium salt polymer supported bimetallic monatomic catalyst, and a preparation method and application thereof. The quaternary phosphonium salt polymer supported bimetallic monatomic catalyst comprises a first metal active component, a second metal active component and a quaternary phosphonium salt polymer carrier; the first metal active component and the second metal active component are supported on the quaternary phosphonium salt polymer support; wherein the first metal active component is a mononuclear complex of a metal I; the second metal active component is a mononuclear complex of a metal II; the quaternary phosphonium salt polymer carrier is obtained by a quaternary phosphonium salt polymer; the quaternary phosphonium salt polymer is obtained by polymerization reaction of quaternary phosphonium salt containing carbon-carbon double bonds; the metal I is selected from at least one of Rh, Ir and Au; the metal II is at least one selected from Ni, La, Ru, Co and Mn. The quaternary phosphonium salt polymer supported bimetallic monatomic catalyst has high carbonylation activity and stability.

Description

Quaternary phosphonium salt polymer loaded bimetallic monatomic catalyst, preparation method and application
Technical Field
The application relates to a quaternary phosphonium salt polymer supported bimetallic monatomic catalyst, a preparation method and application thereof, and belongs to the field of catalyst synthesis.
Background
Methyl acetate is increasingly replacing acetone, butanone, ethyl acetate, cyclopentane, etc. internationally. Because it does not limit the discharge of organic pollutants, it can reach the new environmental standard of paint, printing ink, resin and adhesive factories. The synthesis of ethanol by methyl acetate hydrogenation is also one of the main ways for preparing ethanol by coal at present. The preparation method mainly comprises (1) directly carrying out esterification reaction on acetic acid and methanol by taking sulfuric acid as a catalyst to generate a methyl acetate crude product, then dehydrating by using calcium chloride, neutralizing by using sodium carbonate, and fractionating to obtain a methyl acetate finished product. (2) Dimethyl ether is synthesized by carbonylation on an H-MOR molecular sieve catalyst, but the carbon deposition of the molecular sieve is seriously inactivated, and the space-time yield is lower. (3) When the methanol is carbonylated to prepare the acetic acid, the methyl acetate exists as a byproduct, but the selectivity is low and the separation cost is high. The vast majority of the current commercially viable methyl acetate synthesis routes go through the intermediate step of acetic acid.
At present, the methanol carbonylation process is dominant in the industrial production of acetic acid, in the process, a homogeneous catalyst is commonly used in the prior art, and due to the defects that active components are easy to lose, the separation is difficult and the like in the homogeneous catalyst, some researchers aim at a load type heterogeneous catalyst system. The heterogeneous catalysis system can achieve the characteristics that the catalyst and the product are convenient to separate, the concentration of the catalyst is not limited by solubility, and the like, and can improve the productivity and the like by increasing the concentration of the catalyst. The supported heterogeneous catalyst system can be roughly divided into a polymer carrier, an activated carbon carrier, an inorganic oxide carrier and the like according to different carriers, but the supported catalyst system has the problems of lower activity than that of the homogeneous catalyst system, easy removal of active ingredients, higher requirement on the carrier and the like.
The use of polymers in the carbonylation of methanol in the prior art is still relatively rare and not mature enough. Modified phosphine ligands have been reported to be useful for methanol carbonylation, but have poor stability due to fewer anchor ligands. At present, for the methanol carbonylation reaction system, the most important thing is to find a ligand with better stability or a phosphonium salt polymer containing an ionic bond, and enough metal points (coordination points or cation sites) capable of being anchored on the polymer.
Disclosure of Invention
According to one aspect of the application, a quaternary phosphonium salt polymer loaded bimetallic monatomic catalyst for preparing methyl acetate and acetic acid by methanol heterogeneous carbonylation is provided, a polymer carrier not only has stronger coordination bond effect with a metal mononuclear complex (organic complex), but also forms an ionic bond through positive phosphonium in a framework and a metal mononuclear anion complex (inorganic complex), so that metal monoatomic is dispersed, the carrier has large specific surface area and excellent thermal stability, and the heterogeneous reaction condition required by carbonylation can be met. The quaternary phosphonium salt polymer supported bimetallic monatomic catalyst has high carbonylation activity and stability.
A quaternary phosphonium salt polymer supported bimetallic monatomic catalyst comprises a first metal active component, a second metal active component and a quaternary phosphonium salt polymer carrier; the first metal active component and the second metal active component are supported on the quaternary phosphonium salt polymer support; wherein the first metal active component is a mononuclear complex of a metal I; the second metal active component is a mononuclear complex of a metal II; the quaternary phosphonium salt polymer carrier is obtained by a quaternary phosphonium salt polymer; the quaternary phosphonium salt polymer is obtained by polymerization reaction of quaternary phosphonium salt containing carbon-carbon double bonds; the metal I is selected from at least one of Rh, Ir and Au; the metal II is at least one selected from Ni, La, Ru, Co and Mn.
The mononuclear complex of the metal I is obtained through a metal I complex;
the mononuclear complex of the metal II is obtained by a metal II complex.
Specifically, the mononuclear complex of the metal i may be a mononuclear inorganic complex of the metal i or a mononuclear organic complex of the metal i. The mononuclear complex of the metal II is a mononuclear inorganic complex of the metal II. The organic complex is coordinated with the P ligand in the carrier through a coordination bond, and the inorganic complex is an anionic complex and is connected with positive phosphonium in the polymer carrier skeleton through an ionic bond.
By metal monoatomic is meant that the metal is distributed in the form of a mononuclear nucleus.
Preferably, the metal I in the first metal active component is any one of Au and Ir; the metal II in the second metal active component is any one of Ru and La, and the space-time yield of methyl acetate can reach more than 4200.
Optionally, the quaternary phosphonium salt containing carbon-carbon double bonds is selected from any one of substances with the structural formula shown in the formula I;
Figure BDA0002829296390000031
wherein, in formula I, R1、R2、R3Independently selected from any one of groups containing carbon-carbon double bonds;
R4is selected from C1～C5Any one of an alkyl group and a C6-C10 aryl group;
x is any one of F, Cl, Br and I.
Alternatively, in formula I, R1、R2、R3Independently selected from C containing a carbon-carbon double bond2～C15Any of the groups.
Optionally, the group containing the carbon-carbon double bond is selected from any one of groups with a structural formula shown in a formula II;
Figure BDA0002829296390000032
wherein, in formula II, m is 0 or 1, n is 0 or 1;
R5is selected from C1～C5Any of alkylene groups.
Optionally, the quaternary phosphonium salt containing a carbon-carbon double bond includes at least one of tris (4-vinylphenyl) ylphosphine methyl iodide, tris (4-vinylphenyl) ylphosphine ethyl iodide, tris (4-vinylphenyl) ylphosphine phenyl iodide, tris (4-propenylphenyl) phosphinyl methyl iodide, tris (4-butenylphenyl) phosphinyl methyl iodide, tris (4-propenylphenyl) phosphinyl ethyl iodide, tris (4-propenylphenyl) phosphinyl phenyl iodide, tris (4-butenylphenyl) phosphinyl phenyl iodide, triacrylateylphosphine methyl iodide, triacrylateylphosphine ethyl iodide, triacrylateylphosphine phenyl iodide, tributenylphosphinyl methyl iodide, tripentenylphosphinyl methyl iodide.
The tri (4-vinyl benzene) phosphine methyl iodide has the following structural formula
Figure BDA0002829296390000041
Alternatively, the quaternary phosphonium salt polymer has a hierarchical pore structure comprising macropores, mesopores, and micropores.
Optionally, the quaternary phosphonium salt polymer has a pore volume of 0.1 to 5.0cm3(ii)/g; the specific surface area is 300-3000 m2(ii)/g; the average pore diameter is 0.2 to 50.0 nm.
Alternatively, the first and second metal active components are supported on the quaternary phosphonium salt polymer support by ionic and/or coordinative bonds.
Specifically, the first metal active component and the second metal active component are supported on the quaternary phosphonium salt polymer support through ionic bonds and coordinate bonds, or both the first metal active component and the second metal active component are supported on the quaternary phosphonium salt polymer support through ionic bonds.
Optionally, the first metal active component is present in the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst in an amount of 0.01 to 5.0 wt%; the content of the second metal active component in the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst is 0.1-10 wt%;
wherein the mass of the first metal active component is calculated by the mass of the metal I; the mass of the second metal active component is calculated by the mass of the metal II; the mass of the quaternary phosphonium salt polymer supporting the bimetallic monatomic catalyst is based on the mass of the quaternary phosphonium salt polymer.
Preferably, the content of the first metal active component in the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst is 0.1 to 2.0 wt%.
Optimally, the content of the first metal active component in the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst is 0.3-1.0 wt%
Preferably, the content of the second metal active component in the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst is 0.1 to 4.0 wt%.
Most preferably, the second metal active component is present in the quaternary phosphonium salt polymer-supported bimetallic monatomic catalyst in an amount of 0.2 to 1.0 wt%.
Optionally, the molar ratio of the first metal active component to the second metal active component is 0.1-10; the molar amount of the first metal active component is calculated by the molar amount of the metal I; the molar amount of the second metal active component is calculated by the molar amount of the metal II.
According to another aspect of the present application, there is also provided a method of making the quaternary phosphonium salt polymer-supported bimetallic monatomic catalyst of any of the above, the method comprising:
s100, obtaining a quaternary phosphonium salt polymer;
s200, loading a metal I complex and a metal II complex on the quaternary phosphonium salt polymer to obtain the quaternary phosphonium salt polymer loaded bimetallic monatomic catalyst.
Optionally, the step S100 includes:
thermally polymerizing a mixture containing an initiator, a quaternary phosphonium salt containing carbon-carbon double bonds and an organic solvent a in a solvent to obtain a solution a containing the quaternary phosphonium salt polymer;
and (c) removing the solvent in the solution a to obtain the quaternary phosphonium salt polymer.
Optionally, the initiator is selected from one or more of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile and azobisisoheptonitrile.
Optionally, the organic solvent a is selected from one or more of benzene, toluene, dichloromethane, tetrahydrofuran, methanol, dimethylformamide and chloroform.
Optionally, the mass ratio of the quaternary phosphonium salt containing carbon-carbon double bonds to the initiator is 0.5-100: 1.
Specifically, the upper limit of the mass ratio of the quaternary phosphonium salt having a carbon-carbon double bond to the initiator is 1:1, 10: 1. 20:1, 40:1, 60:1, 80:1, 100: 1; the lower limit of the mass ratio of the quaternary phosphonium salt containing a carbon-carbon double bond to the initiator is 0.5:1, 1:1, 10: 1. 20:1, 40:1, 60:1, 80: 1.
Preferably, the mass ratio of the quaternary phosphonium salt containing carbon-carbon double bonds to the initiator is 30-50: 1.
More preferably, the mass ratio of the quaternary phosphonium salt containing a carbon-carbon double bond to the initiator is 40: 1.
Alternatively, the conditions of the solvent thermal polymerization: the reaction temperature is 80-200 ℃; the reaction time is 1-100 hours.
Specifically, the upper limit of the reaction temperature is selected from 100 ℃, 150 ℃, 200 ℃; the lower limit of the reaction temperature is selected from 80 ℃, 100 ℃ and 150 ℃.
The upper limit of the reaction time is selected from 12h, 24h, 36h, 48h, 60h, 80h and 100 h; the lower limit of the reaction time is selected from 1h, 12h, 24h, 36h, 48h, 60h and 80 h.
Preferably, the reaction temperature is 80-120 ℃; the reaction time is 20-30 h.
More preferably, the reaction temperature is 100 ℃; the reaction time was 24 h.
Specifically, the step S100 includes:
a) mixing quaternary phosphonium salt (monomer) with carbon-carbon double bond with organic solvent a at 0-200 ℃ under the protection of inert atmosphere, adding a free radical initiator, stirring the obtained mixed solution for 0.1-100 hours,
b) transferring the mixed solution into a hydrothermal kettle under the protection of inert atmosphere at the temperature of 0-200 ℃, standing for 1-100 hours under the condition of solvent thermal polymerization to carry out polymerization reaction,
c) the reaction mixture obtained in step b) is subjected to vacuum removal of the solvent at room temperature to obtain a quaternary phosphonium salt polymer having a large surface area and a hierarchical pore structure.
Optionally, the step S200 includes:
s200-a, loading the metal I complex onto the quaternary phosphonium salt polymer to obtain an intermediate product;
s200-b, obtaining a metal II complex;
s200-c, loading the metal II complex onto the intermediate product to obtain the quaternary phosphonium salt polymer loaded bimetallic monatomic catalyst;
wherein, in step S200-a, the metal I complex includes any one of carbonyl chloride of metal I and acetylacetone complex of metal I.
In particular, the carbonyl chloride of metal I comprises Rh2(CO)4Cl2、Ir(CO)3Any one of Cl.
Acetylacetone complexes of metals I including Rh (CO) C5H7O2、Ir(CO)C5H7O2Any one of the above.
In step 200-b, the metal II complex is a metal II anionic complex.
Optionally, the step S200-a includes: and (2) dissolving the metal I complex into an organic solvent b at the temperature of 0-200 ℃ under the protection of an inert atmosphere, adding the quaternary phosphonium salt polymer, stirring, and removing the organic solvent b to obtain the intermediate product.
Optionally, in step S200-a, the organic solvent b is selected from one or more of benzene, toluene, dichloromethane, tetrahydrofuran, methanol, ethanol, dimethylformamide, and chloroform.
Alternatively, in step S200-a, the mass ratio of the metal I complex to the quaternary phosphonium salt polymer is 0.01 to 0.05.
Specifically, the upper limit of the mass ratio of the metal i complex to the quaternary phosphonium salt polymer is selected from 0.015, 0.0285, 0.04, 0.05; the lower limit of the mass ratio of the metal I complex to the quaternary phosphonium salt polymer is selected from 0.01, 0.015, 0.0285, 0.04.
Optionally, step S200-b comprises: and (3) carrying out complex reaction on the mixed solution containing the metal II precursor and the solvent c to obtain a solution containing a metal II complex.
Optionally, the metal ii precursor comprises at least one of a chloride of metal ii, a nitrate of metal ii.
In particular, the chloride of metal II comprises NiCl2、LaCl3、RuCl3、MnCl2、CoCl2Any one of the above.
The nitrate of metal II includes Ni (NO)3)2、La(NO3)3、Mn(NO3)2、Co(NO3)2Any one of the above.
The metal II precursor is complexed with a solvent c to give an anionic complex, e.g. NiCl2Complexing with concentrated hydrochloric acid to obtain NiCl4 2-Complexing ions.
Optionally, the solvent c comprises any one of concentrated hydrochloric acid and nitric acid;
wherein the mass fraction of the concentrated hydrochloric acid is 36-38%.
Optionally, the ratio of the metal ii precursor to the solvent c is 0.1: 15-25 g/ml.
The upper limit of the proportional relation between the metal II precursor and the solvent c is selected from 0.1:20g/ml and 0.1:25 g/ml; the lower limit of the proportional relation between the metal II precursor and the solvent c is selected from 0.1:15g/ml and 0.1:20 g/ml.
Optionally, step S200-c comprises:
dipping the intermediate product into the solution containing the metal II complex compound to obtain the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst;
the mass ratio of the metal II complex to the intermediate product is 0.005-0.02;
wherein the mass of the metal II complex is calculated by the mass of the metal II precursor;
the mass of the intermediate product is based on the mass of the quaternary phosphonium salt polymer.
Specifically, the ratio of the intermediate product to the solution containing the metal II complex is 8-12 g: 20 ml.
Specifically, the upper limit of the mass ratio of the metal II complex to the intermediate product is 0.01, 0.02; the lower limits of the mass ratio of the metal II complex to the intermediate product were 0.005 and 0.01.
Optionally, the step S200 includes:
s200-i, obtaining a solution containing a metal I complex and a metal II complex;
s200-ii, adding the quaternary phosphonium salt polymer into the solution in the step S200-i, and carrying to obtain the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst;
wherein, in step 200-i, the metal I complex is a metal I anionic complex; the metal II complex is a metal II anionic complex.
Optionally, the step S200-i includes:
and mixing the metal I precursor, the metal II precursor and the solvent d, and carrying out a complexing reaction to obtain the solution containing the metal I complex and the metal II complex.
Optionally, the metal I precursor comprises at least one of a chloride of the metal I and a nitrate of the metal I.
Specifically, the chloride of metal I includes HAuCl4、H2IrCl6、IrCl3、RhCl3Any one of the above.
The nitrate of the metal I includes Rh (NO)3)3。
The metal II precursor comprises at least one of chloride of metal II and nitrate of metal II.
Specifically, the chloride of the metal II and the nitrate of the metal II are described above, and are not described in detail herein.
Optionally, the solvent d comprises any one of concentrated hydrochloric acid and nitric acid;
wherein the mass fraction of the concentrated hydrochloric acid is 36-38%.
Optionally, the ratio of the metal I precursor, the metal II precursor and the solvent d is 0.1-0.3 g: 0.05-0.2 g: 15-25 ml.
Optionally, in the step S200-ii, the ratio of the quaternary phosphonium salt polymer to the metal i precursor and the metal ii precursor is 8 to 12 g: 0.1-0.3 g: 0.05 to 0.2 g.
The catalyst formed by two kinds of metal mononuclear anion complexes (inorganic complexes) has higher activity in the methanol heterogeneous carbonylation reaction, and the space-time yield can reach more than 5600.
According to a third aspect of the application, the application of the quaternary phosphonium salt polymer supported bimetallic monoatomic catalyst obtained by the preparation method of any one of the above and the quaternary phosphonium salt polymer supported bimetallic monoatomic catalyst obtained by the preparation method of any one of the above in the preparation of methyl acetate and acetic acid through methanol carbonylation is further provided.
According to a fourth aspect of the present application there is also provided a process for the manufacture of methyl acetate and acetic acid by heterogeneous methanol carbonylation, the process comprising: the raw material containing methanol and CO contacts and reacts with a catalyst to obtain methyl acetate and acetic acid;
the catalyst is selected from any one of the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst described in any one of the above and the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst obtained by the production method described in any one of the above.
Optionally, the reaction conditions are: the reaction temperature is 130-250 ℃; the reaction pressure is 0.5-3.5 MPa.
Optionally, a cocatalyst is also included in the reaction process;
the cocatalyst comprises any one of methyl iodide and methyl bromide.
Optionally, the addition amount of the cocatalyst is 1-40.0 wt% of the methanol.
Optionally, the liquid volume space velocity is 0.1-15 h-1(ii) a The liquid is a methanol and cocatalyst mixture;
the molar ratio of CO to methanol is 1-2.
In this application, C1～C5、C2～C15、C6～C10Wherein the subscript denotes the number of carbon atoms contained in the group, e.g. C5The alkyl group means an alkyl group having 5 carbon atoms;
"alkylene" refers to a group formed by the loss of any two hydrogen atoms from an alkane compound molecule
"arylene" refers to a group formed by the loss of any two hydrogen atoms from the aromatic ring of an aromatic hydrocarbon compound molecule.
The beneficial effects that this application can produce include:
compared with the existing methanol carbonylation technology loaded with rhodium or iridium based reagent, the bimetallic monatomic catalyst loaded with the quaternary phosphonium salt polymer has higher activity (the space-time yield can be improved by 26-180%) and extremely high stability in the methanol heterogeneous carbonylation reaction.
Drawings
FIG. 1 is a physisorption characterization of the catalyst in example 1 of the present application.
FIG. 2 is a spherical aberration electron microscope single atom characterization of the catalyst in example 1 of the present application.
FIG. 3 shows the results of the test of the catalyst of example 1 of the present application in the gas phase carbonylation of methanol.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
Possible embodiments are described below:
a quaternary phosphonium salt polymer supported bimetallic monatomic catalyst for preparing methyl acetate and acetic acid by carbonylating methanol and a preparation method thereof. The main active component is a mononuclear complex of Rh, Ir or Au, and the auxiliary agent is a mononuclear complex of Ni, La, Ru, Co and Mn; the carrier is a phosphine-containing polymer, and the specific surface area of the carrier is 300-3000 m2(ii)/g, the average pore diameter is 0.2 to 50.0 nm.
Wherein the content of the main active component is 0.01-5.0% of the weight of the catalyst; the auxiliary agent is a mononuclear complex of Ni, La, Ru, Co and Mn, and the content of the auxiliary agent is 0.1-10% of the weight of the catalyst; the molar ratio of the main active component to the auxiliary agent is 0.1-10; the metal precursor is selected from one or more of chloride, carbonyl chloride, nitrate, acetylacetone complex, etc., and the solvent can be one or more of concentrated hydrochloric acid, dichloromethane, tetrahydrofuran or dimethylformamide.
Adding a polymer carrier into a solvent containing a metal precursor under 273-473K inert gas protection atmosphere; stirring the obtained mixture solution for 0.1-100 hours; and washing and filtering the obtained reaction mixture by using the same solvent at room temperature, and then removing the solvent in vacuum to obtain the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst.
The CO and the pumped reactants such as methanol and the like enter a fixed bed reactor filled with the catalyst of the invention to carry out methanol carbonylation reaction, and the main products are methyl acetate and acetic acid.
The temperature of the carbonylation reaction is 130-250 ℃, the pressure is 0.5-3.5 MPa, and the liquid volume space velocity is 0.1-15 h-1。
The cocatalyst reactant also comprises methyl iodide which accounts for 1-40.0% of the weight of the methanol.
The main reactor is made of hastelloy.
A quaternary phosphonium salt polymer supported bimetallic monatomic catalyst for carbonylation of methanol is used in the reaction of converting methanol/CO into methyl acetate and acetic acid by using methanol/CO as a raw material.
The quaternary phosphonium salt polymer is preferably prepared by the following method:
firstly, adding a free radical initiator into a vinyl-functionalized triphenyl quaternary phosphonium salt phosphine monomer organic solvent in a 273-473K three-neck round-bottom flask equipped with a stirring and temperature control device under the protection of inert gas such as nitrogen or argon, wherein the weight ratio of the monomer to the free radical initiator is 0.5: 1-100: 1. The obtained mixture solution is stirred for 0.1 to 100 hours. Wherein, preferably, the organic solvent used can adopt one or a mixture of toluene, dichloromethane, tetrahydrofuran or dimethylformamide; the radical initiator may be one of azobisisobutyronitrile and azobisisoheptonitrile. And then, transferring the mixture solution into a closed reactor such as a hydrothermal kettle, and standing the solution for 1-100 hours by using a solvent thermal polymerization method under the protection of 293-473K and inert gas such as nitrogen or argon, thereby generating the required polymer carrier with high surface area and a multi-polar pore structure. And finally, vacuumizing the polymerized reaction mixture at room temperature to remove the solvent, thereby obtaining the high-surface-area quaternary phosphonium salt polymer carrier with the multi-polar-hole structure.
Comparative example 1
At 298K and N2Under a protective atmosphere, 10.0g of tris (4-vinylbenzene) ylphosphine methyl iodide (manufactured by Oratin) as a monomer was dissolved in 100.0ml of a dimethylformamide solvent, 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, and the mixture was stirred for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to remove the solvent to obtain the polymerized quaternary phosphonium salt polymer carrier with the large surface area and the hierarchical pore structure. Then, at 298K and N2Under the protection atmosphere, 0.285gIr (CO)3Cl in 50ml CH3CH2OH, 10g of polymer are added thereto and stirred at room temperature for 24h, CH2Cl2And after washing and suction filtration, vacuumizing and pumping away the solvent to obtain the Ir monatomic iridium-based catalyst loaded on the quaternary phosphonium salt polymer, wherein the content of the Ir complex in the sample is 1.75 wt%.
Example 1
At 298K and N2Under a protective atmosphere, 10.0g of tris (4-vinylbenzene) ylphosphine methyl iodide as a monomer was dissolved in 100.0ml of a dimethylformamide solvent, and 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, followed by stirring for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to obtain the polymerized quaternary phosphonium salt polymer with the large surface area and the hierarchical pore structure, wherein the quaternary phosphonium salt polymer is marked as a carrier # 1.
Then, at 298K and N2Under protective atmosphere, 0.285g of Rh2(CO)4Cl2Dissolved in 50ml CH2Cl210g of the polymer (support # 1) was added thereto and stirred at room temperature for 24 hours, CH2Cl2After washing and suction filtration, the solvent is pumped out in a vacuum mode to obtain an intermediate product.
0.1g of NiCl2Dissolving in 20ml concentrated hydrochloric acid (the concentration is 36 wt%), soaking the prepared sample (namely the intermediate product) in the solution, stirring for 24 hours at room temperature, washing with ethanol, filtering, and drying in vacuum at 90 ℃ to obtain the Rh-Ni bimetallic monatomic catalyst loaded by the quaternary phosphonium salt polymer, wherein the Rh-Ni bimetallic monatomic catalyst is marked as sample No. 1.
The content of the first metal active component Rh complex in sample No. 1 was 1.5 wt%;
the content of the second metal active component Ni complex in sample # 1 was 0.45 wt%;
the molar ratio of Rh complex to Ni complex was 1.9.
The No. 1 catalyst in the example 1 is subjected to physical adsorption characterization, the characterization result is shown in FIG. 1, and the physical structure of the catalyst with large specific surface area and porosity can be seen from FIG. 1;
the 1# catalyst in example 1 is characterized by a single atom by a spherical aberration electron microscope, and the characterization result is shown in fig. 2, and it can be seen from fig. 2 that all metals exist in the form of a single atom.
Example 2
At 298K and N2Under a protective atmosphere, 10.0g of tris (4-vinylbenzene) ylphosphine ethyl iodide (manufacturer: avadin) as a monomer was dissolved in 100.0ml of a dimethylformamide solvent, 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, and the mixture was stirred for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to obtain the polymerized quaternary phosphonium salt polymer with the large surface area and the hierarchical pore structure, wherein the quaternary phosphonium salt polymer is marked as a carrier No. 2.
Then, at 298K and N2Under the protection atmosphere, 0.285gIr (CO)3Cl in 50ml CH3CH2OH, 10g of polymer (support # 2) was added thereto and stirred at room temperature for 24h, CH2Cl2After washing and suction filtration, the solvent is pumped out in a vacuum mode to obtain an intermediate product.
0.1g of NiCl2Dissolving in 20ml of concentrated hydrochloric acid (the concentration is 36 wt%), soaking the prepared sample (namely the intermediate product) in the concentrated hydrochloric acid, stirring for 24 hours at room temperature, washing with ethanol, performing suction filtration, and performing vacuum drying at 90 ℃ to obtain the IrNi bimetallic single-atom catalyst loaded by the quaternary phosphonium salt polymer, wherein the IrNi bimetallic single-atom catalyst is marked as sample No. 2.
The content of the first metal active component Ir complex in sample 2# was 1.75 wt%;
the content of the second metal active component Ni complex in sample 2# was 0.44 wt%.
Example 3
At 298K and N2Under a protective atmosphere, 10.0g of tris (4-vinylbenzene) phenylphosphinyl iodide (manufacturer: avastin) as a monomer was dissolved in 100.0ml of a dimethylformamide solvent, and 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, followed by stirring for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours at 373K under the protection of nitrogen gas by a solvent thermal polymerization method. To be treatedAnd cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to remove the solvent to obtain the polymerized quaternary phosphonium salt polymer with the large surface area and the hierarchical pore structure, wherein the quaternary phosphonium salt polymer is marked as a carrier No. 3.
Then, at 298K and N2Under the protection atmosphere, 0.285gIr (CO)3Cl in 50ml CH3CH2OH, 10g of polymer (support # 3) was added thereto and stirred at room temperature for 24 hours, CH2Cl2After washing and suction filtration, the solvent is pumped out in a vacuum mode to obtain an intermediate product.
0.1g of LaCl3Dissolving in 20ml of concentrated hydrochloric acid (the concentration is 36 wt%), soaking the prepared sample (namely the intermediate product) in the solution, stirring for 24 hours at room temperature, washing with ethanol, filtering, and drying in vacuum at 90 ℃ to obtain the IrLa bimetallic single-atom catalyst loaded by the quaternary phosphonium salt polymer, wherein the IrLa bimetallic single-atom catalyst is marked as sample No. 3.
The content of the first metal active component Ir complex in sample 3# was 1.75 wt%;
the content of the second metal active component La complex in sample # 3 was 0.56% by weight.
Example 4
At 298K and N2Under a protective atmosphere, 10.0g of tris (4-propenylphenyl) ylphosphine methyl iodide (manufacturer: alatin) as a monomer was dissolved in 100.0ml of a dimethylformamide solvent, 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, and the mixture was stirred for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to obtain the polymerized quaternary phosphonium salt polymer with the large surface area and the hierarchical pore structure, wherein the quaternary phosphonium salt polymer is marked as a carrier No. 4.
Then, at 298K and N2Under the protection atmosphere, 0.285gIr (CO)3Cl in 50ml CH3CH2OH, 10g of polymer (i.e. support # 4) was added thereto and stirred at room temperature for 24h, CH2Cl2And after washing and suction filtration, vacuumizing to remove the solvent to obtain an intermediate product.
Adding 0.1g of RoCl3Dissolved in 20ml of concentrated hydrochloric acid (38% by weight) and prepared as described aboveSoaking a sample (namely an intermediate product) in the solution, stirring for 24 hours at room temperature, washing with ethanol, filtering, and drying in vacuum at 90 ℃ to obtain the Ir-Ru bimetallic monatomic catalyst loaded by the quaternary phosphonium salt polymer, wherein the Ir-Ru bimetallic monatomic catalyst is marked as a sample No. 4.
The content of the first metal active component Ir complex in sample # 4 was 1.75 wt%;
the content of the second metal active component Ru complex in sample 4# was 0.48 wt%.
Example 5
At 298K and N2Under a protective atmosphere, 10.0g of tris (4-butenylphenyl) ylphosphine methyl iodide (manufacturer: aradine) as a monomer was dissolved in 100.0ml of a dimethylformamide solvent, 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, and the mixture was stirred for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to obtain the polymerized quaternary phosphonium salt polymer with the large surface area and the hierarchical pore structure, wherein the quaternary phosphonium salt polymer is marked as a carrier No. 5.
Then, at 298K and N2Under protective atmosphere, 0.285g of Rh2(CO)4Cl2Dissolved in 50ml CH3CH2OH, 10g of polymer (i.e. support # 5) was added thereto and stirred at room temperature for 24h, CH2Cl2After washing and suction filtration, the solvent is pumped out in vacuum, and an intermediate product is obtained.
0.1g of LaCl3Dissolving in 20ml concentrated hydrochloric acid (concentration is 38 wt%), soaking the prepared sample (namely intermediate product) in the solution, stirring for 24h at room temperature, washing with ethanol, filtering, and drying in vacuum at 90 ℃ to obtain the Rh-La bimetallic monatomic catalyst loaded by the quaternary phosphonium salt polymer, wherein the Rh-La bimetallic monatomic catalyst is marked as sample No. 5.
The content of the first metal active component Rh complex in sample No. 5 was 1.50 wt%;
the content of the second metal active component La complex in sample # 5 was 0.56% by weight.
Example 6
At 298K and N2Under a protective atmosphere, 10.0g of tris (4-propenylphenyl) phosphineEthyl iodide (manufacturer: Allantin) as a monomer was dissolved in 100.0ml of dimethylformamide as a solvent, and 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, followed by stirring for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to obtain the polymerized quaternary phosphonium salt polymer with the large surface area and the hierarchical pore structure, wherein the quaternary phosphonium salt polymer is marked as a carrier No. 6.
Then, at 298K and N2Under protective atmosphere, 0.285g of Rh2(CO)4Cl2Dissolved in 50ml CH3CH2OH, 10g of polymer (i.e., support No. 6) was added thereto, and stirred at room temperature for 24 hours, CH2Cl2After washing and suction filtration, the solvent is pumped out in a vacuum mode to obtain an intermediate product.
0.1g of MnCl2Dissolving in 20ml concentrated hydrochloric acid (the concentration is 36 wt%), soaking the prepared sample (namely the intermediate product) in the concentrated hydrochloric acid, stirring for 24 hours at room temperature, washing with ethanol, filtering, and drying in vacuum at 90 ℃ to obtain the RhMn bimetallic monatomic catalyst loaded by the quaternary phosphonium salt polymer, wherein the RhMn bimetallic monatomic catalyst is marked as sample No. 6.
The content of the first metal active component Rh complex in sample No. 6 was 1.50 wt%;
the content of the second metal active component Mn complex in sample 6# was 3.45 wt%.
Example 7
At 298K and N2Under a protective atmosphere, 10.0g of tris (4-propenylphenyl) phenylphosphinyl iodide as a monomer was dissolved in 100.0ml of a dimethylformamide solvent, and 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, followed by stirring for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to obtain the polymerized quaternary phosphonium salt polymer with the large surface area and the hierarchical pore structure, wherein the quaternary phosphonium salt polymer is marked as a carrier No. 7.
Then, at 298K and N2Under protective atmosphere, 0.285g of Rh2(CO)4Cl2Dissolved in 50ml CH3CH2OH, 10g of polymer (i.e., support No. 7) was added thereto, and stirred at room temperature for 24 hours, CH2Cl2After washing and suction filtration, the solvent is pumped out in a vacuum mode to obtain an intermediate product.
0.1g of CoCl2Dissolving in 20ml of concentrated hydrochloric acid (the concentration is 37 wt%), soaking the prepared sample (namely the intermediate product) in the concentrated hydrochloric acid, stirring for 24 hours at room temperature, washing with ethanol, filtering, and drying in vacuum at 90 ℃ to obtain the quaternary phosphonium salt polymer-supported RhCo bimetallic monatomic catalyst which is marked as sample No. 7.
The content of the first metal active component Rh complex in sample No. 7 was 1.50 wt%;
the content of the second metal active component Co complex in sample 7# was 4.54 wt%.
Example 8
At 298K and N2Under a protective atmosphere, 10.0g of tris (4-butenylphenyl) phenylphosphinyl iodide as a monomer was dissolved in 100.0ml of a dimethylformamide solvent, and 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, followed by stirring for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to obtain the polymerized quaternary phosphonium salt polymer with the large surface area and the hierarchical pore structure, wherein the quaternary phosphonium salt polymer is marked as a carrier No. 8.
0.285g of HAuCl4And 0.1g of LaCl3Dissolving in 20ml concentrated hydrochloric acid (the concentration is 36 wt%), adding 10g of polymer (namely carrier No. 8), stirring for 24h at room temperature, washing with ethanol, filtering, and drying in vacuum at 90 ℃ to obtain the Au-La bimetallic monatomic catalyst loaded by the quaternary phosphonium salt polymer, wherein the Au-La bimetallic monatomic catalyst is marked as sample No. 8.
The content of the first metal active component Au complex in sample No. 8# was 1.12 wt%;
the content of the second metal active component La complex in sample No. 8# was 0.56 wt%.
Example 9
At 298K and N2Under a protective atmosphere, 10.0g of tripropylphosphine methyl iodide as a monomer was dissolvedTo the above solution, 0.25g of azobisisobutyronitrile as a radical initiator was added in 100.0ml of dimethylformamide solvent, and stirred for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to obtain the polymerized quaternary phosphonium salt polymer with the large surface area and the hierarchical pore structure, wherein the quaternary phosphonium salt polymer is marked as a carrier No. 9.
0.285g of HAuCl4And 0.1 gGluCl3Dissolving in 20ml concentrated hydrochloric acid (the concentration is 36 wt%), adding 10g of polymer (carrier No. 9), stirring at room temperature for 24h, washing with ethanol, filtering, and vacuum drying at 90 ℃ to obtain the Au-Ru bimetallic monatomic catalyst loaded by the quaternary phosphonium salt polymer, wherein the Au-Ru bimetallic monatomic catalyst is marked as a sample No. 9.
The content of the first metal active component Au complex in sample # 9 was 1.12 wt%;
the content of the second metal active component Ru complex in sample # 9 was 0.48 wt%.
Example 10
At 298K and N2Under a protective atmosphere, 10.0g of tripropylphosphine ethyl iodide (manufacturer: alatin) as a monomer was dissolved in 100.0ml of a dimethylformamide solvent, and 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, followed by stirring for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to obtain the polymerized quaternary phosphonium salt polymer with the large surface area and the hierarchical pore structure, wherein the quaternary phosphonium salt polymer is marked as a carrier No. 10.
0.285g of HAuCl4And 0.1g of NiCl2Dissolving in 20ml of concentrated hydrochloric acid (the concentration is 37 wt%), adding 10g of polymer (namely the carrier No. 10), stirring for 24 hours at room temperature, washing with ethanol, filtering, and drying in vacuum at 90 ℃ to obtain the Au-Ni bimetallic monatomic catalyst loaded by the quaternary phosphonium salt polymer, wherein the Au-Ni bimetallic monatomic catalyst is marked as a sample No. 10.
The content of the first metal active component Au complex in sample 10# was 1.12 wt%;
the content of the second metal active component Ni complex in sample 10# was 0.45 wt%.
Example 11
At 298K and N2Under a protective atmosphere, 10.0g of triphenylphosphinylphenyliodide (manufacturer: alatin) as a monomer was dissolved in 100.0ml of a dimethylformamide solvent, and 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, followed by stirring for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to obtain the polymerized quaternary phosphonium salt polymer with the large surface area and the hierarchical pore structure, wherein the quaternary phosphonium salt polymer is marked as a carrier No. 11.
0.285g of IrCl3And 0.1g of LaCl3Dissolving in 20ml concentrated hydrochloric acid (the concentration is 38 wt%), adding 10g of polymer (namely carrier No. 11), stirring for 24h at room temperature, washing with ethanol, filtering, and drying in vacuum at 90 ℃ to obtain the Ir-La bimetallic monatomic catalyst loaded by the quaternary phosphonium salt polymer, wherein the Ir-La bimetallic monatomic catalyst is marked as sample No. 11.
The content of the first metal active component Ir complex in sample 11# was 1.75 wt%;
the content of the second metal active component La complex in sample No. 11 was 0.56% by weight.
Example 12
At 298K and N2Under a protective atmosphere, 10.0g of tributenylphosphine methyliodide (manufacturer: arantine) as a monomer was dissolved in 100.0ml of a dimethylformamide solvent, and 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, followed by stirring for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to obtain the polymerized quaternary phosphonium salt polymer with the large-surface-area hierarchical pore structure, wherein the quaternary phosphonium salt polymer is marked as a carrier No. 12.
0.285g of IrCl3And 0.1g of GluCl3Dissolving in 20ml concentrated hydrochloric acid (concentration of 36 wt%), adding 10g polymer (i.e. carrier # 12), stirring at room temperature for 24 hr, washing with ethanol, vacuum drying at 90 deg.CAnd drying to obtain the Ir-Ru bimetallic monatomic catalyst loaded by the quaternary phosphonium salt polymer, and marking as a sample No. 12.
The content of the first metal active component Ir complex in sample 12# was 1.75 wt%;
the content of the second metal active component Ru complex in sample 12# was 0.48 wt%.
Example 13 characterization of the Quaternary phosphonium salt Polymer
Physical adsorption characterization of quaternary phosphonium salt polymer supported bimetallic monatomic catalyst
The quaternary phosphonium salt polymer samples of examples 1 to 12 were subjected to the specific surface area test and the pore diameter test on an Autosorb-1 adsorption analyzer of Quantachrome Instruments, respectively, and the samples were pretreated at 373K for 20 hours before the test. The test result shows that: the specific surface area of the quaternary phosphonium salt polymer is 300-3000 m2(ii)/g; the average pore diameter is 0.2 to 50.0 nm.
Taking the quaternary phosphonium salt polymer of example 1 as an example, the test results were: the quaternary phosphonium salt polymer has a specific surface area of 1200m2(ii)/g; the average pore diameter was 1.26 nm.
Application example: the prepared catalyst is applied to the reaction of preparing methyl acetate and acetic acid by taking methanol/CO as raw materials.
The reaction conditions are as follows: 200 ℃, 2.5MPa, CH3OH/CO ═ 1: 1.5 (molar ratio), CH3OH/CH3The mass ratio of I to I is 8:1, the liquid feed rate is 0.05ml/min (the liquid volume space velocity is 6.0 h)-1) The mass of the catalyst was 0.1000 g. After the reaction tail gas is cooled by a cold trap, the gas phase product is analyzed on line, and a chromatographic instrument comprises Agilent 7890AGC, a PQ packed column and a TCD detector. Off-line analysis of liquid phase product, FFAP capillary chromatographic column, FID detector. And (4) performing internal standard analysis, wherein isobutanol is used as an internal standard substance.
Methyl acetate and acetic acid were prepared according to the above procedure using the quaternary phosphonium salt polymer supported catalyst prepared in comparative example 1 and examples 1 to 12, and the carbonylation activity, methyl acetate selectivity and acetic acid selectivity are shown in Table 1, and the data is measured after 100 hours. The data for example 1 is shown in figure 3.
TABLE 1 results of the methanol carbonylation reaction of the examples
Figure BDA0002829296390000181
Figure BDA0002829296390000191
Wherein acetic acid selectivity is acetic acid moles/(acetic acid moles + methyl acetate moles);
methyl acetate selectivity ═ methyl acetate moles/(moles of acetic acid + moles of methyl acetate);
space time yield ═ time yield (moles acetic acid + moles methyl acetate)/(moles quaternary phosphonium salt polymer loaded first metal)/reaction time.
The results show that the activity (i.e., the space-time yield) of the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst is much better than that of the quaternary phosphonium salt polymer supported monatomic catalyst, as can be seen by comparing examples 1-12 with comparative example 1.
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 quaternary phosphonium salt polymer supported bimetallic monatomic catalyst is characterized by comprising a first metal active component, a second metal active component and a quaternary phosphonium salt polymer carrier;
the first metal active component and the second metal active component are supported on the quaternary phosphonium salt polymer support;
wherein the first metal active component is a mononuclear complex of a metal I;
the second metal active component is a mononuclear complex of a metal II;
the metal I is selected from at least one of Rh, Ir and Au;
the metal II is at least one selected from Ni, La, Ru, Co and Mn.
2. The quaternary phosphonium salt polymer-supported bimetallic monatomic catalyst of claim 1 wherein the quaternary phosphonium salt polymer support is derived from a quaternary phosphonium salt polymer; the quaternary phosphonium salt polymer is obtained by polymerization reaction of quaternary phosphonium salt containing carbon-carbon double bonds;
preferably, the quaternary phosphonium salt containing carbon-carbon double bonds is selected from any one of substances with the structural formula shown in the formula I;
Figure FDA0002829296380000011
wherein, in formula I, R1、R2、R3Independently selected from any one of groups containing carbon-carbon double bonds;
R4is selected from C1～C5Alkyl radical, C6～C10Any of aryl groups;
x is any one of F, Cl, Br and I;
in formula I, R1、R2、R3Independently selected from C containing a carbon-carbon double bond2～C15Any of the groups;
preferably, said C containing a carbon-carbon double bond2～C15The group is any one of groups with a structural formula shown in a formula II;
Figure FDA0002829296380000021
wherein, in formula II, m is 0 or 1, n is 0 or 1;
R5is selected from C1～C5Any of alkylene groups;
preferably, the quaternary phosphonium salt having a carbon-carbon double bond includes at least one of tris (4-vinylphenyl) ylphosphine methyl iodide, tris (4-vinylphenyl) ylphosphine ethyl iodide, tris (4-vinylphenyl) ylphosphine phenyl iodide, tris (4-propenylphenyl) phosphinyl methyl iodide, tris (4-butenylphenyl) phosphinyl methyl iodide, tris (4-propenylphenyl) phosphinyl ethyl iodide, tris (4-propenylphenyl) phosphinyl phenyl iodide, tris (4-butenylphenyl) phosphinyl phenyl iodide, tripropyl phosphinyl methyl iodide, tripropyl phosphinyl ethyl iodide, tripropyl phosphinyl phenyl iodide, tributenylphosphine methyl iodide, tripentenylphosphinyl methyl iodide.
3. The quaternary phosphonium salt polymer-supported bimetallic monatin catalyst of claim 1, wherein the quaternary phosphonium salt polymer has a hierarchical pore structure including macropores, mesopores, and micropores;
preferably, the quaternary phosphonium salt polymer has a pore volume of 0.1 to 5.0cm3(ii)/g; the specific surface area is 300-3000 m2(ii)/g; the average pore diameter is 0.2 to 50.0 nm.
4. The supported bimetallic monatomic catalyst of claim 1, wherein the first metal active component and the second metal active component are supported on the quaternary phosphonium salt polymer support via ionic and/or coordinate bonds.
5. The quaternary phosphonium salt polymer-supported bimetallic monatomic catalyst of claim 1, wherein the first metal active component is present in the quaternary phosphonium salt polymer-supported bimetallic monatomic catalyst in an amount of 0.01 to 5.0 wt%;
the content of the second metal active component in the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst is 0.1-10 wt%;
wherein the mass of the first metal active component is calculated by the mass of the metal I;
the mass of the second metal active component is calculated by the mass of the metal II;
the mass of the quaternary phosphonium salt polymer loaded with the bimetallic monatomic catalyst is based on the mass of the quaternary phosphonium salt polymer;
preferably, the molar ratio of the first metal active component to the second metal active component is 0.1-10;
the molar amount of the first metal active component is calculated by the molar amount of the metal I;
the molar amount of the second metal active component is calculated by the molar amount of the metal II.
6. The method of preparing the quaternary phosphonium salt polymer-supported bimetallic monatomic catalyst of any one of claims 1 to 5, wherein the method comprises:
s100, obtaining a quaternary phosphonium salt polymer;
s200, loading a metal I complex and a metal II complex on the quaternary phosphonium salt polymer to obtain the quaternary phosphonium salt polymer loaded bimetallic monatomic catalyst.
7. The method according to claim 6, wherein the step S200 includes:
s200-a, loading the metal I complex onto the quaternary phosphonium salt polymer to obtain an intermediate product;
s200-b, obtaining a metal II complex;
s200-c, loading the metal II complex onto the intermediate product to obtain the quaternary phosphonium salt polymer loaded bimetallic monatomic catalyst;
wherein, in step S200-a, the metal I complex comprises any one of carbonyl chloride of metal I and acetylacetone complex of metal I;
in step 200-b, the metal II complex is a metal II anionic complex;
preferably, the step S200-a includes: under the condition of 0-200 ℃ and protection of an inactive atmosphere, dissolving a metal I complex into an organic solvent b, adding the quaternary phosphonium salt polymer, stirring, and removing the organic solvent b to obtain an intermediate product;
preferably, in step S200-a, the organic solvent b is selected from one or more of benzene, toluene, dichloromethane, tetrahydrofuran, methanol, ethanol, dimethylformamide and chloroform;
preferably, in the step S200-a, the mass ratio of the metal I complex to the quaternary phosphonium salt polymer is 0.01 to 0.05;
preferably, step S200-b comprises: carrying out complex reaction on the mixed solution containing the metal II precursor and the solvent c to obtain a solution containing a metal II complex;
preferably, the metal II precursor comprises at least one of a chloride of the metal II and a nitrate of the metal II;
preferably, the solvent c includes any one of concentrated hydrochloric acid and nitric acid;
wherein the mass fraction of the concentrated hydrochloric acid is 36-38%;
preferably, the ratio of the metal II precursor to the solvent c is 0.1: 15-25 g/ml;
preferably, step S200-c comprises:
dipping the intermediate product into the solution containing the metal II complex to obtain the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst;
the mass ratio of the metal II complex to the intermediate product is 0.005-0.02;
wherein the mass of the metal II complex is calculated by the mass of the metal II precursor;
the mass of the intermediate product is based on the mass of the quaternary phosphonium salt polymer.
8. The method according to claim 6, wherein the step S200 includes:
s200-i, obtaining a solution containing a metal I complex and a metal II complex;
s200-ii, adding the quaternary phosphonium salt polymer into the solution in the step S200-i, and carrying to obtain the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst;
wherein, in step 200-i, the metal I complex is a metal I anionic complex; the metal II complex is a metal II anionic complex;
preferably, the step S200-i includes:
mixing a metal I precursor, a metal II precursor and a solvent d, and carrying out a complexing reaction to obtain a solution containing a metal I complex and a metal II complex;
preferably, the metal I precursor comprises at least one of chloride of metal I and nitrate of metal I;
the metal II precursor comprises at least one of chloride of metal II and nitrate of metal II;
preferably, the solvent d includes any one of concentrated hydrochloric acid and nitric acid;
wherein the mass fraction of the concentrated hydrochloric acid is 36-38%;
preferably, the ratio of the metal I precursor, the metal II precursor and the solvent d is 0.1-0.3 g: 0.05-0.2 g: 15-25 ml;
preferably, in the step S200-ii, the ratio of the quaternary phosphonium salt polymer to the metal i precursor and the metal ii precursor is 8 to 12 g: 0.1-0.3 g: 0.05 to 0.2 g.
9. Use of the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst described in any one of claims 1 to 5 or the quaternary phosphonium salt polymer supported bimetallic monatomic catalyst obtained by the production method described in any one of claims 6 to 8 for the production of methyl acetate and acetic acid by the carbonylation of methanol.
10. A process for the heterogeneous carbonylation of methanol to produce methyl acetate and acetic acid comprising: the raw material containing methanol and CO contacts and reacts with a catalyst to obtain methyl acetate and acetic acid;
the catalyst is selected from any one of the quaternary phosphonium salt polymer supported bimetallic monoatomic catalyst according to any one of claims 1 to 5 and the quaternary phosphonium salt polymer supported bimetallic monoatomic catalyst obtained by the production method according to any one of claims 6 to 8;
preferably, the reaction conditions are: the reaction temperature is 130-250 ℃; the reaction pressure is 0.5-3.5 MPa;
preferably, a cocatalyst is also included in the reaction process;
the cocatalyst comprises any one of methyl iodide and methyl bromide;
preferably, the addition amount of the cocatalyst is 1-40.0 wt% of the methanol;
preferably, the liquid volume space velocity is 0.1-15 h-1；
The liquid is a methanol and cocatalyst mixture;
the molar ratio of CO to methanol is 1-2.
CN202011456302.1A 2020-11-20 2020-12-11 Quaternary phosphonium salt polymer loaded bimetallic monatomic catalyst, preparation method and application Pending CN114515604A (en)

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