CN109453814B

CN109453814B - Rhodium Catalyst Supported by Hierarchical Porous Polymer Containing Sulfonic Acid Group and Phosphine Ligand and Its Preparation and Application

Info

Publication number: CN109453814B
Application number: CN201710794650.1A
Authority: CN
Inventors: 吕元; 任周; 丁云杰; 宋宪根
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2017-09-06
Filing date: 2017-09-06
Publication date: 2021-07-27
Anticipated expiration: 2037-09-06
Also published as: CN109453814A

Abstract

本发明提供一种用于甲醇多相羰基化的含磺酸基和膦配体的大表面积多级孔结构聚合物固载的Rh基催化剂及其制备方法。按本发明提供的在一定温度和压力反应条件下CH₃OH/CO转化为乙酸甲酯和乙酸含磺酸基和膦配体的大表面积多级孔结构聚合物固载的铑基催化剂。催化剂由主活性组分和载体两部分组成。主活性组分为铑金属配位化合物；载体为含磺酸基和膦配体的大表面积多级孔结构聚合物。在固定床反应器中，在一定的温度和压力以及本催化剂作用下，CH₃OH/CO可高活性、高选择性地转化为乙酸甲酯。The invention provides an Rh-based catalyst supported by a large surface area hierarchical porous structure polymer containing a sulfonic acid group and a phosphine ligand for the heterogeneous carbonylation of methanol and a preparation method thereof. The invention provides a rhodium-based catalyst for converting CH ₃ OH/CO into methyl acetate and acetic acid containing sulfonic acid groups and phosphine ligands under certain temperature and pressure reaction conditions. The catalyst consists of the main active component and the carrier. The main active component is rhodium metal coordination compound; the carrier is a polymer with large surface area and hierarchical pore structure containing sulfonic acid group and phosphine ligand. In a fixed-bed reactor, CH ₃ OH/CO can be converted into methyl acetate with high activity and high selectivity under certain temperature and pressure and the action of the catalyst.

Description

Multi-level pore polymer supported rhodium catalyst containing sulfonic group and phosphine ligand, preparation and application thereof

Technical Field

The invention belongs to the technical field of heterogeneous catalytic carbonylation, and particularly relates to a large-surface-area hierarchical pore structure polymer-immobilized Rh-based catalyst containing sulfonic acid groups and phosphine ligands and application thereof in methyl acetate and acetic acid preparation reaction through methanol heterogeneous carbonylation.

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.

Currently, the methanol carbonylation process dominates in the industrial production of acetic acid, and the production capacity of the current acetic acid production device adopting the process accounts for 94 percent of the total production capacity of acetic acid. The industrial process for the carbonylation of methanol to produce acetic acid has gone through roughly three stages of development over the past 50 years:

the first stage is as follows: the BSAF company first achieved the commercial production of acetic acid by the methanol carbonylation process using a cobalt catalyst at relatively high reaction temperatures and pressures (250 ℃, 60MPa) in 1960. And a second stage: the company Monsanto developed rhodium-iodides (RhI) with higher activity and selectivity₃) A catalytic system. The reaction temperature and pressure were also relatively low (about 175 ℃ C., 3.0MPa), and the selectivity of acetic acid based on methanol was 99% or more, and the selectivity based on CO was also 90% or more. The corrosion resistance of the device is very high, and a full zirconium alloy reaction kettle is needed. And a third stage: the industrialization of Ir catalysts is the methanol carbonylation process for the production of acetic acid. The process greatly improves the stability of the catalyst, the reaction is carried out under the condition of lower water content, the generation of liquid by-products is reduced, and the conversion rate of CO is improved.

The company Chiyoda, japan, and UOP jointly developed the acitica process based on a heterogeneous Rh catalyst in which an active Rh complex is chemically immobilized on a polyvinylpyridine resin. The strong and weak coordinate bond chelating polymer catalyst which is formed by researching and combining the Yuan-national Cynanchum Paniculatum of the chemical research institute of Chinese academy of sciences also forms an independent intellectual property system, and the catalyst system has the characteristics of high stability, high activity and the like and can improve the selectivity of CO.

However, since the homogeneous catalyst itself has the disadvantages of easy loss of active components, difficult separation, etc., some researchers have focused on the supported 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 other systems according to different carriers, but the supported catalyst system has the problems of lower activity than the homogeneous catalyst system, easy removal of active ingredients, higher requirement on the carrier and the like. And the methyl acetate preparation with high selectivity by methanol heterogeneous carbonylation directly skips the acetic acid synthesis route, thereby saving the mass production cost. Especially in the direction of using methanol heterogeneous carbonylation as a carrier, as the properties of polymer materials are continuously expanded and optimized, the research and the exploration are continued.

On the other hand, in recent years, porous organic polymers have attracted extensive attention of researchers due to advantages such as controllable chemical and physical properties, simple functionalized synthesis strategies, large specific areas, and low raw material prices, and more porous organic polymers are used as carriers and applied to the field of heterogeneous catalysis, and organic functional groups in monomer components can be modulated, so that various polymer carriers can be purposefully synthesized according to different reaction requirements.

In 2007, germanin et al (chem. mater,2008,20,7069) have also synthesized super-crosslinked polymers of the polyaniline type. They adopt Ullmann and Buherwald coupling reaction to carry out post-crosslinking of copolymerization on polyaniline and phenylenediamine so as to obtain a super-crosslinked polymer taking nitrogen atoms as connecting points. In order to obtain higher specific surface area, germanin et al (j. mater. chem,2007,17,4989) generate post-crosslinking of polyaniline and diiodomethane or paraformaldehyde to form a methylene-linked network structure, a lewis acid catalyst is not needed in the whole reaction process, hydrogen chloride waste gas is not generated, and the specific surface area of the obtained polymer can reach 632m²(ii) in terms of/g. In 2011, Tan Bien professor group (Macromolecules,2011,44,2410) at university of science and technology in Huazhong adopts dimethoxymethane as a cross-linking agent to carry out one-step F-C alkylation on rigid aromatic ring molecules, so as to obtain a super cross-linked polymer with a high specific surface area and a mainly microporous structure. Rigid aromatic ring molecules may include benzene, toluene, chlorobenzene, phenol, biphenyl, triphenylbenzene, and the like. The method has the by-product of only methanol, and the reaction condition is mildAnd, the raw materials are cheap, can be used for large-scale production, most importantly, different skeleton precursor and cross-linking agent proportion can form diversified porous structure, make it have potential using value. In 2012, the Copper group (j.am. chem.soc,2012,134,10741) successfully introduced chiral binaphthol monomers into hypercrosslinked polymers according to this synthetic approach. So far, porous polymers formed by chiral monomers are quite rare, and the development of the porous polymers is mainly limited by low specific surface area of formed materials and complicated synthetic steps, so that the porous polymers are difficult to be practically applied, and the Copper professor directly forms a hypercrosslinked polymer with the chiral binaphthol monomers by utilizing an external crosslinking method and one-step F-C alkylation.

Since the strong electron donating ability of the phosphine or nitrogen ligand in the homogeneous phase leads to a substantial increase in the activity of the Rh center, it would be desirable to be able to use polymers containing phosphine ligands for heterogeneous methanol carbonylation. In fact, in addition to the success of the above-mentioned Acetica process involving the use of immobilized polymers, the use of other polymers in methanol carbonylation is currently relatively rare and immature. However, heterogeneous systems are generally less active than corresponding homogeneous systems. How to correspondingly increase the catalyst activity has been a crucial issue. In general, the activity of the catalyst can be improved by adding some metal or nonmetal auxiliary agents or changing the acid treatment mode. Sulfonation is a research focus at present, sulfonic acid can be used as an auxiliary agent to improve the reactivity of some reactions, so that the improvement of the TOF of the carbonylation reaction can be considered by adding organic sulfonic acid into a polymerized monomer.

Disclosure of Invention

The invention aims to provide a large-surface-area hierarchical pore structure polymer-supported Rh-based catalyst containing sulfonic acid groups and phosphine ligands for heterogeneous carbonylation of methanol and a preparation method thereof. Polymer-supported Rh-based catalysts containing sulfonic acid groups and phosphine ligands have higher carbonylation activity than polymer-supported Rh-based catalysts containing phosphine ligands.

The technical scheme of the invention is as follows:

the catalyst consists of two parts, namely a main active component and a carrier, wherein the active component is an Rh precursor, the carrier is a polymer containing sulfonic acid groups and phosphine ligands, and the specific surface area of the carrier is 300-3000 m²(ii)/g, the average pore diameter is 0.2-50.0 nm;

wherein the content of main active component Rh is 0.1-20.0% of the weight of the catalyst; rh precursor form is RhCl₃、Rh₂(CO)₄Cl₂、RhPO₄、Rh₂(SO₄)₃And Rh (PPh)₃)₃Cl, and the used organic solvent can adopt one or a mixture of more of dichloromethane, tetrahydrofuran or dimethylformamide.

Adding a polymer carrier into an organic solvent containing an Rh precursor under the protection of 273-473K and inert gas, wherein the weight ratio of Rh content to the carrier is 0.01: 1-0.2: 1; stirring the obtained mixture solution for 0.1-100 hours; and washing the obtained reaction mixture with the same solvent at room temperature, performing suction filtration, and removing the solvent in vacuum to obtain the Rh-based catalyst immobilized on the polymer containing sulfonic groups and phosphine ligands.

The preparation method according to claim 8, wherein the reactants of CO and pumped methanol are fed into a fixed bed reactor filled with the catalyst of the present invention to carry out methanol carbonylation reaction, and the main product is methyl acetate.

The temperature of the carbonylation reaction is 130-250 ℃, the pressure is 0.5-3.5MPa, and the liquid volume space velocity is 0.1-15h^-1。

The cocatalyst reactant also comprises methyl iodide which accounts for 1-100.0% of the weight of the methanol.

The volume ratio of hydrogen to CO in the reaction gas is 0.1-2.

The main reactor is made of zirconium.

The Rh-based catalyst immobilized by the polymer containing sulfonic groups and phosphine ligands and used for carbonylation of methanol is used for reaction for converting methanol/CO into methyl acetate and acetic acid by taking methanol/CO as a raw material.

The sulfonic acid group-and phosphine ligand-containing polymer is preferably prepared by the following method:

firstly, adding a free radical initiator into an organic solvent containing P, an alkenyl functionalized organic ligand monomer and a sulfonic acid monomer in a three-neck round-bottom flask equipped with a stirring and temperature control device under 273-473K and inert gas such as nitrogen or argon protection atmosphere, wherein the weight ratio of the phosphine-containing monomer to the free radical initiator is 0.5: 1-100: 1; the weight ratio of the phosphine-containing monomer to the sulfonic acid monomer 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 under the protection of 293-473K and inert gas such as nitrogen or argon by using a solvent thermal polymerization method to enable the organic ligand monomer such as vinyl functionalized triphenylphosphine ligand to generate the required polymer carrier with high surface area and a multipolar pore structure. And (3) vacuumizing the polymerized reaction mixture at room temperature to remove the solvent, finally performing ion exchange in a sulfuric acid solution, washing to be neutral, and vacuumizing to remove the solvent to obtain the high-surface-area Rh-based catalyst carrier which is immobilized by the polymer containing sulfonic groups and phosphine ligands and has a multi-polar pore structure. The specific surface area and pore size distribution of the sample were measured on an Autosorb-1 adsorption analyzer from Quantachrome Instruments. Samples were pretreated at 373K for 20 hours before testing

The invention has the beneficial effects that:

compared with the existing methanol carbonylation technology of the rhodium-based catalyst loaded by the organic phosphine-containing polymer carrier, the Rh-based catalyst loaded by the polymer containing sulfonic acid groups and phosphine ligands has higher activity in the heterogeneous carbonylation reaction of methanol.

In a fixed bed reactor, under the action of certain temperature and pressure and the catalyst, CH₃OH/CO can be converted into methyl acetate with high activity and high selectivity.

Detailed Description

The following examples illustrate but do not limit what is intended to be protected by the present invention.

Example 1 (comparative example)

At 298K and N₂Under a protective atmosphere, 10.0g of tris (4-vinylphenyl) ylphosphine as a monomer was dissolved in 100.0ml of tetrahydrofuran solvent, 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, and stirring was carried out 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 organic ligand polymer carrier with the large-surface-area hierarchical pore structure formed by polymerizing the tri (4-vinyl benzene) phosphine. Then, at 298K and N₂Under a protective atmosphere, 0.0285g of Rh is added₂(CO)₄Cl₂Dissolving in 50ml dichloromethane, adding 5g tri (4-vinyl benzene) phosphine polymer, stirring for 24h at room temperature, washing with dichloromethane, vacuum-pumping to remove solvent, and obtaining the rhodium-based catalyst loaded by the organic phosphine-containing polymer carrier. The technical route of the polymerization of the tri (4-vinylphenyl) phosphine ligand polymer carrier and the loading of metal Rh in the embodiment is shown as follows.

Example 2

At 298K and N₂Under the protection atmosphere, 8g of tris (4-vinylphenyl) phosphine and 5g of sodium 4-vinylbenzenesulfonate as monomers are dissolved in 100.0ml of tetrahydrofuran solvent, 0.325g of azobisisobutyronitrile as a radical initiator is added to the above solution, and stirring is carried outStirring 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. Cooling the solution after polymerization to room temperature, vacuum-pumping the solvent at room temperature, and reacting with 100ml of 1mol/L H under the protection of 295K and nitrogen gas₂SO₄And stirring the aqueous solution for 24 hours, washing the aqueous solution to be neutral, and pumping the solvent in vacuum to obtain the copolymerized large-surface-area hierarchical pore polymer carrier. Then, at 298K and N₂Under a protective atmosphere, 0.0285g of Rh is added₂(CO)₄Cl₂Dissolving in 50ml dichloromethane, adding 5g polymer, stirring for 24h at room temperature, washing with dichloromethane, vacuum-pumping to remove solvent, and getting Rh-based catalyst carried by polymer containing sulfonic group and phosphine ligand. The technical route of polymerization of the polymer carrier and loading of metallic Rh in this example is shown below.

Example 3

At 298K and N₂8g of bis (4-vinylbenzene) phenylphosphine and 5g of sodium 4-vinylbenzenesulfonate as monomers were dissolved in 100.0ml of a dimethylformamide solvent under a protective atmosphere, 0.325g of azobisisoheptonitrile as a radical initiator was added to the above solution, 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. Cooling the solution after polymerization to room temperature, vacuum-pumping the solvent at room temperature, and reacting with 100ml of 1mol/L H under the protection of 295K and nitrogen gas₂SO₄And stirring the aqueous solution for 24 hours, washing the aqueous solution to be neutral, and pumping the solvent in vacuum to obtain the copolymerized large-surface-area hierarchical pore polymer carrier. Then, at 298K and N₂Under a protective atmosphere, 0.0350g of RhCl is added₃Dissolving in 50ml of tetrahydrofuran, adding 5g of polymer, stirring for 24h at room temperature, washing with tetrahydrofuran, filtering, vacuumizing, and removing solvent to obtain the Rh-based catalyst immobilized by the polymer containing sulfonic groups and phosphine ligands. The polymer support in this example polymerizes and supports goldThe technical route of Rh is shown as follows.

Example 4

At 298K and N₂Under a protective atmosphere, 8g of 4-vinylphenyldiphenylphosphine and 5g of sodium 4-vinylbenzenesulfonate as monomers were dissolved in 100.0ml of a methylene chloride solvent, and 0.325g of azobisisoheptonitrile 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. Cooling the solution after polymerization to room temperature, vacuum-pumping the solvent at room temperature, and reacting with 100ml of 1mol/L H under the protection of 295K and nitrogen gas₂SO₄And stirring the aqueous solution for 24 hours, washing the aqueous solution to be neutral, and pumping the solvent in vacuum to obtain the copolymerized large-surface-area hierarchical pore polymer carrier. Then, at 298K and N₂Under the protection atmosphere, 0.0325g of RhPO is added₄Dissolving in 50ml of dimethylformamide, adding 5g of polymer into the dimethylformamide, stirring for 24h at room temperature, washing with the dimethylformamide, carrying out suction filtration, and then vacuumizing to remove the solvent to obtain the rhodium-based catalyst loaded by the polymer carrier. The technical route of polymerization of the polymer carrier and loading of metallic Rh in this example is shown below.

Example 5

At 298K and N₂8g of trivinylphosphine and 5g of sodium 4-vinylbenzenesulfonate as monomers were dissolved in 100.0ml of a toluene solvent under a protective atmosphere, 0.325g of azobisisoheptonitrile 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. Cooling the polymerized solution to room temperature, vacuum-pumping the solvent at room temperature, and reacting with the solution under the protection of 295K and nitrogen gas100ml 1mol/L H₂SO₄And stirring the aqueous solution for 24 hours, washing the aqueous solution to be neutral, and pumping the solvent in vacuum to obtain the copolymerized large-surface-area hierarchical pore polymer carrier. Then, at 298K and N₂Under the protection atmosphere, 0.0315g Rh₂(SO₄)₃Dissolving in 50ml dichloromethane, adding 5g polymer, stirring for 24h at room temperature, washing with dichloromethane, vacuum-pumping to remove solvent, and getting rhodium-based catalyst loaded by polymer carrier. The technical route of polymerization of the polymer carrier and loading of metallic Rh in this example is shown below.

Example 6

At 298K and N₂Under a protective atmosphere, 8g of tris (4-vinylbenzene) phosphine and 8g of sodium 4-vinylbenzene sulfonate as monomers were dissolved in 100.0ml of a tetrahydrofuran solvent, and 0.4g 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. Cooling the solution after polymerization to room temperature, vacuum-pumping the solvent at room temperature, and reacting with 100ml of 1mol/L H under the protection of 295K and nitrogen gas₂SO₄And stirring the aqueous solution for 24 hours, washing the aqueous solution to be neutral, and pumping the solvent in vacuum to obtain the copolymerized large-surface-area hierarchical pore polymer carrier. Then, at 298K and N₂Under a protective atmosphere, 0.0285g of Rh is added₂(CO)₄Cl₂Dissolving in 50ml dichloromethane, adding 5g polymer, stirring for 24h at room temperature, washing with dichloromethane, vacuum-pumping to remove solvent, and getting rhodium-based catalyst loaded by polymer carrier. The technical route of the polymerization of the polymer carrier and the loading of the metal Rh in the present example is similar to that of example 2.

Example 7

At 298K and N₂Under a protective atmosphere, 8g of tris (4-vinylphenyl) phosphine and 5g of sodium 4-styrylbenzenesulfonate as monomers were dissolved in 100.0ml of tetrahydrofuran solvent0.325g of azobisisobutyronitrile as a radical initiator was added to the solution, 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. Cooling the solution after polymerization to room temperature, vacuum-pumping the solvent at room temperature, and reacting with 100ml of 1mol/L H under the protection of 295K and nitrogen gas₂SO₄And stirring the aqueous solution for 24 hours, washing the aqueous solution to be neutral, and pumping the solvent in vacuum to obtain the copolymerized large-surface-area hierarchical pore polymer carrier. Then, at 298K and N₂Under a protective atmosphere, 0.0285g of Rh (PPh)₃)₃And dissolving Cl in 50ml of dichloromethane, adding 5g of polymer into the dichloromethane, stirring for 24 hours at room temperature, washing and filtering the dichloromethane, and vacuumizing to remove the solvent to obtain the rhodium-based catalyst loaded by the polymer carrier. The technical route of polymerization of the polymer carrier and loading of metallic Rh in this example is shown below.

Example 8

At 298K and N₂8g of tris (4-vinylphenyl) phosphine and 5g of sodium 2, 4-divinylbenzene sulfonate as monomers were dissolved in 100.0ml of tetrahydrofuran solvent under a protective atmosphere, 0.325g of azobisisobutyronitrile as a radical initiator was added to the above solution, and stirring was carried out 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. Cooling the solution after polymerization to room temperature, vacuum-pumping the solvent at room temperature, and reacting with 100ml of 1mol/L H under the protection of 295K and nitrogen gas₂SO₄And stirring the aqueous solution for 24 hours, washing the aqueous solution to be neutral, and pumping the solvent in vacuum to obtain the copolymerized large-surface-area hierarchical pore polymer carrier. Then, at 298K and N₂Under a protective atmosphere, 0.0285g of Rh is added₂(CO)₄Cl₂Dissolving in 50ml dichloromethane, adding 5g polymer, stirring for 24h at room temperature, washing with dichloromethane, vacuum-pumping to remove solvent, and getting rhodium-based catalyst loaded by polymer carrier. This exampleThe technical route of polymerization of the polymer carrier and loading of metallic Rh is shown as follows.

Example 9

At 298K and N₂Under a protective atmosphere, 8g of trivinylphosphine and 5g of sodium 2, 4-divinylbenzene sulfonate as monomers were dissolved in 100.0ml of tetrahydrofuran solvent, 0.325g of azobisisobutyronitrile as a radical initiator was added to the above solution, and stirring was carried out 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. Cooling the solution after polymerization to room temperature, vacuum-pumping the solvent at room temperature, and reacting with 100ml of 1mol/L H under the protection of 295K and nitrogen gas₂SO₄And stirring the aqueous solution for 24 hours, washing the aqueous solution to be neutral, and pumping the solvent in vacuum to obtain the copolymerized large-surface-area hierarchical pore polymer carrier. Then, at 298K and N₂Under a protective atmosphere, 0.0285g of Rh is added₂(CO)₄Cl₂Dissolving in 50ml dichloromethane, adding 5g polymer, stirring for 24h at room temperature, washing with dichloromethane, vacuum-pumping to remove solvent, and getting rhodium-based catalyst loaded by polymer carrier. The technical route of polymerization of the polymer carrier and loading of metallic Rh in this example is shown below.

Example 10

At 298K and N₂8g of bis (4-vinylphenyl) phenylphosphine and 5g of 4-sodium styrylbenzenesulfonate were dissolved as monomers in 100.0ml of tetrahydrofuran solvent under a protective atmosphere, 0.325g 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. Cooling the solution after polymerization to room temperatureThe solvent is removed in vacuo and then the mixture is mixed with 100ml of 1mol/L H under an atmosphere of 295K and nitrogen gas₂SO₄And stirring the aqueous solution for 24 hours, washing the aqueous solution to be neutral, and pumping the solvent in vacuum to obtain the copolymerized large-surface-area hierarchical pore polymer carrier. Then, at 298K and N₂Under a protective atmosphere, 0.0285g of Rh is added₂(CO)₄Cl₂Dissolving in 50ml dichloromethane, adding 5g polymer, stirring for 24h at room temperature, washing with dichloromethane, vacuum-pumping to remove solvent, and getting rhodium-based catalyst loaded by polymer carrier. The technical route of polymerization of the polymer carrier and loading of metallic Rh in this example is shown below.

Application example: the prepared catalyst is applied to the reaction for preparing methyl acetate by taking methanol/CO as a raw material.

The reaction conditions are as follows: 195 deg.C, 2.5MPa, CH₃OH/CO ═ 1: 1.5 (molar ratio), CH₃OH/CH₃I (mass ratio) 8:1, liquid feed rate 0.05ml/min, catalyst mass 0.1000 g. After the reaction tail gas is cooled by a cold trap, the gas product is analyzed on line, and the chromatographic instruments are Agilent 7890A GC, PQ packed columns and TCD detectors. 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 polymer supported rhodium-based catalysts prepared in examples 1-8, and the carbonylation TOF, methyl acetate selectivity and acetic acid selectivity are shown in table 1.

TABLE 1 results of the methanol carbonylation reaction of the examples

Examples	TOF_acetyl/h^-1	Acetic acid selectivity (%)	Methyl acetate selectivity (%)
				1	1500	7.1	92.9
2	3800	12	88
				3	3700	10	90
4	3400	9.7	90.3
				5	1800	7.7	92.3
6	4200	15	85
				7	3500	9.9	90.1
8	3550	10.2	89.8
				9	1600	6.9	93.1
10	2900	8.9	91.1

The results show that the carbonylation activity of the polymer carrier supported rhodium-based catalyst containing sulfonic acid groups and phosphine ligands is far higher than that of the sulfur-free rhodium-based catalyst system supported by the organic phosphine-containing polymer carrier through comparison of 1-10, and the carbonylation activity is relatively higher to a certain extent when the sulfur content is higher.

The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It will be understood by those skilled in the art that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.

Claims

1. the application of sulfonic acid group and phosphine ligand-containing hierarchical porous polymer immobilized rhodium catalyst in heterogeneous methanol carbonylation to prepare methyl acetate reaction, it is characterized in that: described rhodium-based catalyst is composed of main active component and The carrier is composed of two parts, the main active component is Rh, and the carrier is a polymer; Rh accounts for 0.01-5.0wt% of the total mass of the catalyst;

The carrier is a polymer formed by copolymerization of a vinyl monomer containing a phosphine ligand and a vinyl-containing sulfonate monomer; the reaction temperature is 130-250° C., and the reaction pressure is 0.5-3.5 MPa;

The volume space velocity of the reaction liquid is 0.1-15h ^-1 , and the molar ratio of CO and methanol is 1-2;

The reaction raw material includes methyl iodide as a co-catalyst, and the amount of the co-catalyst added is 20-100.0 wt % of methanol.

2. according to the described application of claim 1, it is characterized in that: Rh accounts for 0.1-4.0wt% of catalyst gross mass.

3. The application according to claim 1, characterized in that: Rh accounts for 0.2-1.0 wt% of the total mass of the catalyst.

4. according to the application according to claim 1, it is characterized in that: described organic ligand polymer carrier has the hierarchical pore structure that comprises macropore, mesopore and micropore, and their proportioning is 5%～20%: 40~70%:10%~55%, the pore volume is 0.1~5.0cm ³ /g, the pore size distribution is 0.2~50.0nm, and the specific surface area is 300~3000m ² /g.

5. according to the described application of claim 1, it is characterized in that: the preparation method of described sulfonic acid group-containing and phosphine ligand polymer carrier comprises,

a) Under the protective atmosphere of 273~473K and inert atmosphere, in the organic solvent of vinyl monomer containing phosphine ligand and sulfonate monomer containing vinyl, add a free radical initiator, which contains phosphine ligand The weight ratio of the vinyl monomer and the free radical initiator is 0.5:1~100:1; the weight ratio of the vinyl monomer containing the phosphine ligand and the sulfonate monomer containing the vinyl group is 0.5:1~ 100:1; and the resulting mixture solution was stirred for 0.1 to 100 hours;

b) Under the protective atmosphere of 273~473K and inert gas atmosphere, transfer the mixture solution in step a) into a hydrothermal kettle and stand for 1~100 hours under the condition of solvothermal polymerization at 333~423K to carry out the polymerization reaction ;

c) The reaction mixture obtained in step b) is vacuumed to remove the solvent at room temperature, thereby obtaining an organic ligand polymer carrier with a large surface area and a hierarchical pore structure.

6. according to the application described in claim 5, it is characterized in that, the organic solvent used in step a) is a solvent selected from benzene, toluene, dichloromethane, tetrahydrofuran, methyl alcohol, dimethylformamide and chloroform One or more than two; the free radical initiator is selected from cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptanenitrile. One or more than two; the vinyl monomers containing phosphine ligands are tristyryl phosphine, bis(4-vinylphenyl) phenyl phosphine, 4-vinylphenyl diphenyl phosphine, tristyryl phosphine One or more of vinylphosphine; the vinyl-containing sulfonate ligand is 4-vinylbenzene sulfonate sodium, 4-styrene benzene sulfonate sodium, 2,4-divinylbenzene One or more of sodium sulfonate.

7. application according to claim 1 is characterized in that: the preparation method of described catalyst comprises:

a) Under the protective atmosphere of 273~473K and inert gas atmosphere, in 1ml~200ml of 0.5~2mol/L H ₂ SO ₄ aqueous solution, add the polymer carrier, and stir the obtained mixture solution for 0.1~100 hours;

b) the reaction mixture obtained in step a) is washed with water at room temperature, filtered to neutrality, and then the solvent is removed in vacuo, thereby obtaining a sulfur-promoted acid-activated organic ligand polymer carrier;

c) under 273～473K and inert atmosphere gas protective atmosphere, in the organic solvent containing Rh precursor, add the organic ligand polymer carrier that sulfur promotes acid activation, and wherein the weight ratio of described Rh content and carrier is 0.01: 1~0.2:1; and the resulting mixture solution was stirred for 0.1~100 hours;

b) the reaction mixture obtained in step c) is washed with the same solvent at room temperature, suction filtered, and then the solvent is removed in vacuo, thereby obtaining a polymer carrier-immobilized rhodium containing a sulfonic acid group and a phosphine ligand base catalyst.

8. application according to claim 7 is characterized in that, the organic solvent used in step c) is a kind of selected from benzene, toluene, dichloromethane, tetrahydrofuran, methyl alcohol, dimethylformamide and chloroform or two or more; the Rh precursor is one or more selected from RhCl ₃ , Rh ₂ (CO) ₄ Cl ₂ , RhPO ₄ , Rh ₂ (SO ₄ ) ₃ and Rh(PPh ₃ ) ₃ Cl .

9 . The application according to claim 1 , wherein the main reactor material used for the reaction is zirconium material. 10 .