CN114558619A - Preparation method of polymer ligand multi-metal cage catalyst and application of catalyst in carbonylation synthesis of acetic acid or acetic anhydride - Google Patents

Preparation method of polymer ligand multi-metal cage catalyst and application of catalyst in carbonylation synthesis of acetic acid or acetic anhydride Download PDF

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CN114558619A
CN114558619A CN202210141392.8A CN202210141392A CN114558619A CN 114558619 A CN114558619 A CN 114558619A CN 202210141392 A CN202210141392 A CN 202210141392A CN 114558619 A CN114558619 A CN 114558619A
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catalyst
ligand
rhodium
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polymer
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CN114558619B (en
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邵守言
闫丰文
朱桂生
代松涛
黄志军
王忠华
袁国卿
刘云梅
许炎
唐丽
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JIANGSU SOPO (GROUP) CO Ltd
JIANGSU SOPO CHEMICAL CO LTD
Institute of Chemistry CAS
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JIANGSU SOPO (GROUP) CO Ltd
JIANGSU SOPO CHEMICAL CO LTD
Institute of Chemistry CAS
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Abstract

The invention belongs to the field of synthesis of acetic acid and acetic anhydride by carbonylation, and discloses a preparation method of a polymer ligand multi-metal cage-shaped catalyst and application of the catalyst in synthesis of acetic acid or acetic anhydride by carbonylation. The invention prepares a micro-crosslinked hydrophilic polymer as a metal rhodium ligand, simultaneously introduces other inorganic metal ions as a cocatalyst, and the system expands to a cage-shaped structure in reaction liquid. The introduction of other inorganic metal ions can effectively reduce the dosage of metal rhodium and the cost of the catalyst, and simultaneously, the comprehensive effect of the system can not bring obvious reduction of catalytic activity and selectivity, so that the catalyst system has the characteristics of low cost, good stability and high efficiency.

Description

Preparation method of polymer ligand multi-metal cage catalyst and application of catalyst in carbonylation synthesis of acetic acid or acetic anhydride
Technical Field
The invention belongs to the field of synthesis of acetic acid and acetic anhydride by carbonylation, and particularly relates to a preparation method of a polymer ligand multi-metal cage-shaped catalyst and application of the catalyst in synthesis of acetic acid or acetic anhydride by carbonylation.
Background
The invention of Paulik et al (US3769329) of Monsanto company in the early 70 th century is that methanol and carbon monoxide are carbonylated under the action of homogeneous rhodium catalyst to prepare acetic acid, and this invention opens up a new important technological route for the oxo synthesis of methanol. On this basis, the subsequent work by Halcon (BE819455) Ealtman, Ajinamoto (Japan Kokai50/30,820), Showa Denko (Japan Kokai50/47,922), BP (B.Von Schlotheim, chem.Industrie1994, 9/89.80) and Hoechst (DE 24560965) has made a breakthrough in the study of the same [ Rh (CO)2I2] -negative ion structure for the carbonylation of methyl acetate to produce acetic anhydride.
With continued improvement and sophistication, the use of homogeneous rhodium as a catalyst for the carbonylation of methanol and methyl acetate has become the most important route to acetic acid and acetic anhydride in the world today. The catalyst has high activity and good selectivity, and is an obvious advantage of the catalyst; however, the instability of such catalysts, which tend to form precipitates of trivalent rhodium, especially at higher temperatures which favor the reaction, or even when the partial carbon monoxide pressure in the flash-separated part is reduced, is well recognized. The design of catalyst structures and the improvement of reaction systems have been the subject of intense research for a long time, and a large number of research papers and patent patents are published every year.
Among them, the most successful example is hoechst celanese company, which developed a low water content oxo synthesis process in the beginning of the 80's of the 20 th century by improving the Monsanto process, and characterized in that a higher content of inorganic iodine salt is added to the reaction system, and the technical advantages of the process are very obvious, and the patent application is US5001259 and EP 055618. Lithium iodide is also the most important catalyst promoter in the reaction system for preparing acetic anhydride by carbonylation of methyl acetate. Joseph R.ZoelletalCatal. today, 1992, 13.73-91, et al, reported an acetic anhydride catalysis system from Eastman corporation, discussed the role of lithium iodide in the reaction, and proposed the reaction mechanism of methyl acetate carbonylation catalyzed by a Li-Rh co-catalysis system.
In recent years, particularly after 2020, the price of noble metal is greatly increased, particularly the price of metal rhodium is increased by nearly 10 times and exceeds the great level of 4000 yuan/g, and as a main catalytic system for producing acetic acid in China, the characteristics of high price and easiness in generating precipitate of a rhodium catalyst become important for acetic anhydride production enterprises. The research of finding a low-cost catalytic system, improving the stability of the existing catalytic system and improving the rhodium recovery technology becomes a hotspot of various enterprise researches.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a polymer ligand polymetallic cage-shaped catalyst and application thereof in carbonylation synthesis of acetic acid or acetic anhydride. The method prepares a micro-crosslinked hydrophilic polymer as a metal rhodium ligand, simultaneously introduces other inorganic metal ions as a cocatalyst, and the system expands to a cage-shaped structure in reaction liquid. The introduction of other inorganic metal ions can effectively reduce the dosage of metal rhodium and the cost of the catalyst, and simultaneously, the comprehensive effect of the system can not bring obvious reduction of catalytic activity and selectivity, so that the catalyst system has the characteristics of low cost, good stability and high efficiency.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
the polymer ligand multi-metal cage catalyst takes a micro-crosslinked polymer as a ligand, the polymer ligand is a copolymer of 2-vinylpyridine, acrylic acid or methacrylic acid and acrylate, which is lightly crosslinked by a crosslinking agent, and the light crosslinking refers to that the crosslinking agent is 0.2-1% of the total mole amount of monomers; the polymer ligand multi-metal cage catalyst takes rhodium and nickel bimetal as active species, and introduces lithium ions as a catalytic assistant for reaction.
The improvement is that the dosage of the 2-vinylpyridine is 15 to 30 percent of the total molar quantity of the monomers, and the dosage of the acrylic acid or the methacrylic acid is 20 to 30 percent of the total molar quantity of the monomers; the dosage of the acrylate monomer is 40-65% of the total molar amount of the monomer.
The improvement is that the crosslinking agent is trimethylolpropane trimethacrylate or divinylbenzene.
The improvement is that the acrylic ester monomer is any one of methyl methacrylate, ethyl methacrylate, methyl acrylate or ethyl acrylate.
The improvement is that the preparation method of the polymer ligand is as follows: mixing 2-vinylpyridine, acrylic acid or methacrylic acid and acrylate monomers with a cross-linking agent, adding the mixture into a benzene solvent, stirring, slowly adding azobisisobutyronitrile with the mole number of 1% of the monomers as an initiator, reacting at 65 ℃ for 1h, cooling the solution, precipitating and filtering with diethyl ether, dissolving with acetone, repeatedly dissolving and precipitating for 3-4 times, and finally placing the solution in vacuum and reducing the pressure to constant weight.
The preparation method of the polymer ligand multi-metal cage catalyst specifically comprises the following steps:
step 1, dissolving 0.03g of lithium hydroxide and 1g of polymer ligand in a 95% ethanol-water mixed solvent by volume fraction, stirring at normal temperature for 1h, adding excessive ether for precipitation, and placing in vacuum and reducing pressure to constant weight to obtain a product A;
step 2, 0.01-0.05g of NiCl is added2Dissolving the product A in ethanol, refluxing for 3h at 50 deg.C under the protection of CO gas, cooling to room temperature, precipitating with excessive diethyl ether, washing the precipitate with 0 deg.C methanol for several times, and vacuum drying to constant weight;
and 3, dissolving the precipitate in methanol, stirring in an ice bath, adding 0.15g of dichlorotetracarbonyl dirhodium simultaneously, continuing stirring for 1h, adding excessive diethyl ether for precipitation, and filtering to obtain the polymer ligand polymetallic cage-shaped catalyst.
The application of the polymer ligand polymetallic cage-shaped catalyst in the synthesis of acetic acid by methanol carbonylation.
As an improvement, the specific steps of the application are as follows: adding a polymer ligand polymetallic cage-shaped catalyst, methanol and methyl iodide into a pressure kettle, introducing carbon monoxide to replace air in the pressure kettle, keeping the pressure of the carbon monoxide at 3-4 MPa and the reaction temperature at 150-200 ℃, and stirring for reaction to obtain acetic acid, wherein the dosage of the polymer ligand polymetallic cage-shaped catalyst in a reaction system is calculated by rhodium, and the rhodium content is 500-2000 PPm; the usage amount of the catalyst promoter methyl iodide in the reaction system is 0.2-5 mol/L.
The application of the polymer ligand polymetallic cage-shaped catalyst in catalyzing carbonylation of methyl acetate to synthesize acetic anhydride.
As an improvement, the specific steps of the application are as follows: adding a polymer ligand polymetallic cage catalyst, methyl acetate, methyl iodide and an acetic acid solvent into a pressure kettle, introducing carbon monoxide to replace air in the pressure kettle, continuously introducing the carbon monoxide and adding hydrogen, wherein the reaction temperature is 170-200 ℃, stirring and reacting to obtain acetic anhydride, and the dosage of the polymer ligand polymetallic cage catalyst in a reaction system is calculated by rhodium, and the rhodium content is 600-1500 PPm; the usage amount of the catalyst promoter methyl iodide in the reaction system is 0.2-5 mol/L; the pressure of the mixed gas of carbon monoxide and hydrogen is 3.5-4.5 MPa, wherein the volume content of hydrogen in the mixed gas is 1-10%.
Has the advantages that:
compared with the prior art, the preparation method of the polymer ligand polymetallic cage-shaped catalyst and the application thereof in the synthesis of acetic acid or acetic anhydride by carbonylation have the following advantages:
the catalyst structure of the invention is basically characterized in that a cage polymer which can be swelled and dispersed in alcohol solvent is prepared as a ligand, and non-noble metal is introduced to form a binary catalyst system. Due to the action of polar molecular groups of the cage-shaped polymer ligand, the violent change of the microenvironment state around the rhodium metal catalytic active center in the flash evaporation process can be delayed to a certain extent, rhodium precipitation is greatly reduced, and the catalytic life is prolonged.
Meanwhile, the introduction of the nickel metal active center greatly reduces the dosage of rhodium metal and the concentration of the rhodium metal active center, reduces the cost of the catalyst and further inhibits rhodium precipitation. Therefore, the catalyst of the invention has excellent catalytic activity and reaction stability when used for catalyzing the carbonylation of methanol to prepare acetic acid and the carbonylation of methyl acetate to prepare acetic anhydride.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
Example 1
Mixing 0.25mol of 2-vinylpyridine, 0.25mol of acrylic acid, 0.5mol of methyl acrylate and a trace amount of cross-linking agent (wherein the cross-linking agent is 0.4% of the total mole amount of the monomers), adding the mixture into a benzene solvent, stirring, slowly adding azobisisobutyronitrile with the mole number of 1% of the monomers as an initiator, reacting for 1h at 65 ℃, cooling the solution, precipitating and filtering by diethyl ether, dissolving by acetone, repeatedly dissolving and precipitating for 3-4 times, and placing the solution in vacuum and reducing the pressure to constant weight to obtain the polymer ligand 1.
Dissolving 0.03g of lithium hydroxide and 1g of polymer ligand 1 in an ethanol-water mixed solvent with volume fraction of 95% (water volume content is 5%), stirring for 1h at normal temperature, adding excessive diethyl ether for precipitation, and placing in vacuum and reducing pressure to constant weight to obtain a product A;
0.03g of NiCl2Dissolving the product A in ethanol, refluxing for 3h under the protection of CO gas at 50 deg.C, cooling to room temperature, precipitating with excessive diethyl ether, washing with 0 deg.C methanol for several times, and vacuum drying to constant weight;
dissolving the precipitate in 50ml of methanol, stirring in an ice bath, simultaneously adding 0.15g of dichlorotetracarbonyl dirhodium, continuously stirring for 1h, adding excessive diethyl ether for precipitation, and filtering to obtain the polymer ligand polymetallic cage catalyst 1.
Example 2
1.34g of polymer ligand polymetallic cage catalyst 1 (the content of rhodium in the solution is about 800ppm), 1.1mol of methanol, 0.2mol of methyl iodide (a cocatalyst) and 0.75mol of acetic acid are added into a 250ml pressure kettle (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process); after carbon monoxide is introduced, the temperature is raised to 150 ℃, the stirring speed is 500 r/min, the reaction pressure is controlled to be 3.5MPa, and the reaction time is 15 min, so that the acetic acid is obtained.
The conversion rate of single methanol is 71.5%, the catalyst is reused for catalytic reaction through a laboratory simulation flash evaporation process, the reaction condition is unchanged, the conversion rate of single methanol can still reach 68.7% after the catalyst is recycled for 50 times, and the attenuation is not obvious. The rhodium content in the reaction solution after the initial and 50 cycles was measured by atomic absorption spectroscopy, and found that the rhodium content still reached 94.1% of the initial state after 50 cycles (the test method was to measure the amount of rhodium in the reaction solution by atomic absorption spectroscopy, and divide the added amount), about 5.9% of rhodium was precipitated and lost.
Comparative example 1
Adding a traditional industrial rhodium catalytic system (namely rhodium triiodide-lithium iodide catalyst, specifically weighing 0.52g of rhodium triiodide and 0.2g of lithium iodide, wherein the rhodium content of the solution is about 1000ppm), 1.1mol of methanol, 0.2mol of methyl iodide and 0.75mol of acetic acid (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process) into a 250ml pressure kettle; and introducing carbon monoxide for repeated replacement, heating to 150 ℃, stirring at 500 revolutions per minute, controlling the reaction pressure to be 3.5MPa, and reacting for 15 minutes to obtain the acetic acid.
The conversion rate of single methanol is 72.3%, the catalyst is reused for catalytic reaction through a laboratory simulation flash evaporation process, the reaction condition is unchanged, the conversion rate of single methanol is 60.7% after the catalyst is recycled for 50 times, and the attenuation is obvious. The rhodium content in the reaction solution after the initial and the 50 times of circulation tests by atomic absorption spectroscopy, and the rhodium content still reaches 78.3% of that in the initial state after the 50 times of circulation, and about 21.7% of rhodium is precipitated and lost.
As can be seen from comparative example 2 and comparative example 1: the polymer ligand multi-metal cage catalyst system can still achieve the catalytic effect of the traditional catalyst with the rhodium concentration of 1000ppm in the initial state under the condition that the rhodium concentration is about 800ppm, has better stability, circulates for 50 times, and has far lower rhodium loss rate than the traditional catalyst. The catalytic system can reduce the dosage of rhodium, maintain higher catalytic activity and obviously inhibit the precipitation of rhodium.
Example 3
0.81g of polymer ligand polymetallic cage catalyst 1 (the content of rhodium in the solution is about 500ppm), 1.1mol of methanol, 0.02mol of methyl iodide and 1.12mol of acetic acid are added into a 250ml pressure kettle (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process); introducing carbon monoxide, heating to 170 ℃, stirring at 500 r/min, controlling the reaction pressure to be 4.0MPa, and reacting for 30 min to obtain the acetic acid.
The conversion rate of single methanol is 52.3%, the catalyst is reused for catalytic reaction through a laboratory simulation flash evaporation process, the reaction condition is unchanged, the conversion rate of single methanol can still reach 51.7% after the catalyst is recycled for 50 times, and the attenuation is not obvious. The rhodium content in the reaction solution after the initial and 50 cycles of the atomic absorption spectroscopy test was found to be 95.6% of that in the initial state after 50 cycles (the test method is to measure the amount of rhodium in the reaction solution by the atomic absorption spectroscopy, and divide the added amount), and about 4.4% of rhodium is precipitated and lost.
Example 4
2.4g of polymer ligand polymetallic cage catalyst 1 (the content of rhodium in the solution is about 1500ppm), 0.80mol of methyl acetate, 0.02mol of methyl iodide (a cocatalyst) and 0.25mol of acetic acid are added into a 250ml pressure kettle (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process); replacing air in the pressure kettle with carbon monoxide, continuously introducing the carbon monoxide, adding hydrogen, heating to 185 ℃ under the hydrogen pressure of 0.2MPa, stirring at the speed of 500 r/min, keeping the reaction pressure constant at 4.2MPa, and reacting for 20 min to obtain the acetic anhydride.
The conversion rate of methyl acetate in one time is 47.9%, the catalyst is reused for catalytic reaction through a laboratory simulation flash evaporation process, the reaction condition is unchanged, the conversion rate of methanol in one time can still reach 46.1% after the catalyst is recycled for 50 times, and the attenuation is not obvious. The rhodium content in the reaction solution after the initial and 50 cycles was measured by atomic absorption spectroscopy, and found that the rhodium content still reached 92.2% of the initial state after 50 cycles (the test method was to measure the amount of rhodium in the reaction solution by atomic absorption spectroscopy, and divide the added amount), about 7.8% of rhodium was precipitated and lost.
Example 5
2.5g of polymer ligand polymetallic cage catalyst 1 (the content of rhodium in the solution is about 760ppm), 1.14mol of methanol, 0.80mol of methyl iodide and 1.1mol of acetic acid are added into a 250ml pressure kettle (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process); introducing carbon monoxide, reacting at 175 deg.C under 4.0MPa for 25 min at a stirring speed of 500 rpm to obtain acetic acid.
The conversion rate of single methanol is 87.6%, the catalyst is reused for catalytic reaction through a laboratory simulation flash evaporation process, the reaction condition is unchanged, the conversion rate of single methanol can still reach 84.1% after the catalyst is recycled for 50 times, and the attenuation is not obvious. The rhodium content in the reaction solution after the initial and 50 cycles was measured by atomic absorption spectroscopy, and found that the rhodium content still reached 93.2% of the initial state after 50 cycles (the test method was to measure the amount of rhodium in the reaction solution by atomic absorption spectroscopy, and divide the added amount), about 6.8% of rhodium was precipitated and lost.
Example 6
1.3g of polymer ligand polymetallic cage catalyst 1 (the content of rhodium in the solution is about 800ppm), 0.55mol of methyl acetate, 0.24mol of methyl iodide and 0.55mol of acetic acid are added into a 250ml pressure kettle (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process); after the air in the reaction kettle is replaced by carbon monoxide, introducing hydrogen under the pressure of 0.2MPa, introducing carbon monoxide to control the reaction temperature to be 190 ℃, the total reaction pressure to be 4.5MPa, the stirring speed to be 500 r/min and the reaction time to be 30 min. To obtain acetic anhydride.
The conversion rate of single methyl acetate is 63.1%, the catalyst is reused for catalytic reaction through a laboratory simulation flash evaporation process, the reaction condition is unchanged, the conversion rate of single methanol can still reach 60.7% after the catalyst is recycled for 50 times, and the attenuation is not obvious. The rhodium content in the reaction solution after the initial and 50 cycles was measured by atomic absorption spectroscopy, and found that the rhodium content still reached 93.6% of the initial state after 50 cycles (the test method was to measure the amount of rhodium in the reaction solution by atomic absorption spectroscopy, and divide the added amount), about 6.4% of rhodium was precipitated and lost.
Example 7
0.94g of polymer ligand polymetallic cage catalyst 1 (the content of rhodium in the solution is about 600ppm), 0.5mol of methyl acetate, 0.23mol of methyl iodide and 0.52mol of acetic acid (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process) are added into a 250ml pressure kettle, the air in the reaction kettle is replaced by carbon monoxide, then hydrogen pressure is introduced into the kettle under 0.2MPa, carbon monoxide is added to keep the total reaction pressure at 165 ℃, the stirring speed is 500 r/min, and the reaction time is 18 min. To obtain acetic anhydride.
The conversion rate of methyl acetate in one time is 49.6%, the catalyst is reused for catalytic reaction through a laboratory simulation flash evaporation process, the reaction condition is unchanged, the conversion rate of methanol in one time can still reach 47.5% after the catalyst is recycled for 50 times, and the attenuation is not obvious. The rhodium content in the reaction solution after the initial and 50 cycles was measured by atomic absorption spectroscopy, and found that the rhodium content still reached 93.9% of the initial state after 50 cycles (the test method was to measure the amount of rhodium in the reaction solution by atomic absorption spectroscopy, and divide the added amount), about 6.1% of rhodium was precipitated and lost.
Example 8
3.2g of polymer ligand polymetallic cage catalyst 1 (the content of rhodium in the solution is about 2000ppm), 1.1mol of methanol, 0.1mol of methyl iodide and 0.9mol of acetic acid are added into a 250ml pressure kettle (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process); introducing carbon monoxide, reacting at 175 deg.C under 4.0MPa for 20 min at a stirring speed of 500 rpm to obtain acetic acid.
The conversion rate of single methanol is 93.5%, the catalyst is reused for catalytic reaction through a laboratory simulation flash evaporation process, the reaction condition is unchanged, the conversion rate of single methanol can still reach 91.1% after the catalyst is recycled for 50 times, and the attenuation is not obvious. The rhodium content in the reaction solution after the initial and 50 cycles was measured by atomic absorption spectroscopy, and found that the rhodium content still reached 94.3% of the initial state after 50 cycles (the test method was to measure the amount of rhodium in the reaction solution by atomic absorption spectroscopy, and divide the added amount), about 5.7% of rhodium was precipitated and lost.
Example 9
Mixing 0.15 mol of 2-vinylpyridine, 0.2mol of methacrylic acid, 0.65 mol of methyl methacrylate and a trace amount of cross-linking agent (wherein the cross-linking agent is 0.2 percent of the total mole amount of the monomers), adding the mixture into a benzene solvent, stirring, slowly adding azobisisobutyronitrile with the mole number of 1 percent of the monomers as an initiator, reacting for 1 hour at 65 ℃, cooling the solution, precipitating and filtering by diethyl ether, dissolving by acetone, repeatedly dissolving and precipitating for 3-4 times, and placing the solution in vacuum and reducing the pressure to constant weight to obtain the polymer ligand 2.
Dissolving 0.03g of lithium hydroxide and 1g of polymer ligand 2 in an ethanol-water mixed solvent with the volume fraction of 95% (the volume content of water is 5%), stirring for 1 hour at normal temperature, adding excessive ether for precipitation, and placing in vacuum and reducing pressure to constant weight to obtain a product A2;
0.03g of NiCl2Dissolving the product A2 in ethanol, refluxing for 3h at 50 deg.C under protection of CO gas, cooling to room temperature, precipitating with excessive diethyl ether, washing with 0 deg.C methanol for several times, and vacuum drying to constant weight;
dissolving the precipitate in 50ml of methanol, stirring in an ice bath, simultaneously adding 0.15g of dichlorotetracarbonyl dirhodium, continuing stirring for 1h, adding excessive diethyl ether for precipitation, and filtering to obtain the polymer ligand polymetallic cage catalyst 2.
Example 10
0.81g of polymer ligand polymetallic cage catalyst 2 (the content of rhodium in the solution is about 500ppm), 1.1mol of methanol, 0.02mol of methyl iodide and 1.12mol of acetic acid are added into a 250ml pressure kettle (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process); introducing carbon monoxide, heating to 170 ℃, stirring at the speed of 500 r/min, controlling the reaction pressure to be 4.0MPa, and reacting for 30 min to obtain the acetic acid.
The conversion rate of single methanol is 53.6%, the catalyst is reused for catalytic reaction through a laboratory simulation flash evaporation process, the reaction condition is unchanged, the conversion rate of single methanol can still reach 51.2% after the catalyst is recycled for 50 times, and the attenuation is not obvious. The rhodium content in the reaction solution after the initial and 50 cycles was measured by atomic absorption spectroscopy, and found that the rhodium content still reached 94.7% of the initial state after 50 cycles (the test method was to measure the amount of rhodium in the reaction solution by atomic absorption spectroscopy, and divide the added amount), about 5.3% of rhodium was precipitated and lost.
It can be seen that the degree of crosslinking is reduced, the primary catalytic activity of the catalytic system is slightly increased, but the stability is slightly reduced.
Example 11
Mixing 0.3 mol of 2-vinylpyridine, 0.3 mol of methacrylic acid, 0.4 mol of methyl methacrylate and a trace amount of cross-linking agent (wherein the cross-linking agent is 1% of the total mole amount of the monomers), adding the mixture into a benzene solvent, stirring, slowly adding azobisisobutyronitrile with the mole number of 1% of the monomers as an initiator, reacting for 1h at 65 ℃, cooling the solution, precipitating and filtering by diethyl ether, dissolving by acetone, repeatedly dissolving and precipitating for 3-4 times, and putting the solution in vacuum and reducing the pressure to constant weight to obtain the polymer ligand 3.
Dissolving 0.03g of lithium hydroxide and 1g of polymer ligand 3 in an ethanol-water mixed solvent with the volume fraction of 95% (the volume content of water is 5%), stirring for 1 hour at normal temperature, adding excessive ether for precipitation, and placing in vacuum and reducing pressure to constant weight to obtain a product A3;
0.03g of NiCl2Dissolving the product A3 in ethanol, refluxing for 3h at 50 deg.C under protection of CO gas, cooling to room temperature, precipitating with excessive diethyl ether, washing with 0 deg.C methanol for several times, and vacuum drying to constant weight;
dissolving the precipitate in 50ml of methanol, stirring in an ice bath, simultaneously adding 0.15g of dichlorotetracarbonyl dirhodium, continuing stirring for 1h, adding excessive diethyl ether for precipitation, and filtering to obtain the polymer ligand polymetallic cage catalyst 3.
Example 12
0.81g of polymer ligand polymetallic cage catalyst 3 (the content of rhodium in the solution is about 500ppm), 1.1mol of methanol, 0.02mol of methyl iodide and 1.12mol of acetic acid are added into a 250ml pressure kettle (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process); introducing carbon monoxide, heating to 170 ℃, stirring at the speed of 500 r/min, controlling the reaction pressure to be 4.0MPa, and reacting for 30 min to obtain the acetic acid.
The conversion rate of single methanol is 39.3%, the catalyst is reused for catalytic reaction through a laboratory simulation flash evaporation process, the reaction condition is unchanged, the conversion rate of single methanol can still reach 39.2% after the catalyst is recycled for 50 times, the mol/L.h is high, and the attenuation is not obvious. The rhodium content in the reaction solution after the initial and 50 cycles was measured by atomic absorption spectroscopy, and it was found that the rhodium content still reached 98.9% of the initial state after 50 cycles (the test method was to measure the amount of rhodium in the reaction solution by atomic absorption spectroscopy, divided by the amount added), and about 1.1% of rhodium was precipitated and lost.
It can be seen that the amount of the cross-linking agent is increased to 1% of the total molar amount of the monomers, the degree of cross-linking of the polymer is increased, and the catalytic activity of the catalytic system is significantly reduced, probably because the solution communication between the inside of the polymer and the catalytic mother liquor is limited, but the stability of the catalytic system is slightly and significantly increased.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.

Claims (10)

1. The polymer ligand multi-metal cage catalyst is characterized in that a micro-crosslinked polymer is used as a ligand, the polymer ligand is a copolymer of 2-vinylpyridine, acrylic acid or methacrylic acid and acrylic esters which are lightly crosslinked by using a crosslinking agent, and the light crosslinking refers to that the crosslinking agent is 0.2-1% of the total mole amount of monomers; the polymer ligand multi-metal catalyst takes rhodium and nickel bimetallic as active species, and simultaneously introduces lithium ions as a catalytic assistant for reaction.
2. The polymeric ligand polymetallic cage catalyst of claim 1, wherein the amount of 2-vinylpyridine is 15-30% of the total molar amount of the monomers, and the amount of acrylic acid or methacrylic acid is 20-30% of the total molar amount of the monomers; the dosage of the acrylate monomer is 40-65% of the total molar amount of the monomer.
3. The polymer-ligand multimetallic cage catalyst of claim 1, wherein the crosslinking agent is trimethylolpropane trimethacrylate or divinylbenzene.
4. The polymeric ligand polymetallic cage catalyst as claimed in claim 1, wherein the acrylate monomer is any one of methyl methacrylate, ethyl methacrylate, methyl acrylate or ethyl acrylate.
5. The polymeric ligand multimetallic cage catalyst of claim 1, wherein the polymeric ligand is prepared by the following process: mixing 2-vinylpyridine, acrylic acid or methacrylic acid and acrylate monomers with a cross-linking agent, adding the mixture into a benzene solvent, stirring, slowly adding azodiisobutyronitrile with the mole number of 1% of the monomers as an initiator, reacting at 65 ℃ for 1h, cooling the solution, precipitating and filtering by using ether, dissolving by using acetone, repeatedly dissolving and precipitating for 3-4 times, and finally putting the solution in vacuum and reducing the pressure to constant weight.
6. The method for preparing the polymer ligand multi-metal cage catalyst according to claim 1, which comprises the following steps:
step 1, dissolving 0.03g of lithium hydroxide and 1g of polymer ligand in a 95% ethanol-water mixed solvent by volume fraction, stirring at normal temperature for 1h, adding excessive ether for precipitation, and placing in vacuum and reducing pressure to constant weight to obtain a product A;
step 2, 0.01-0.05g of NiCl is added2Dissolving the product A in ethanol, refluxing for 3h at 50 deg.C under the protection of CO gas, cooling to room temperature, precipitating with excessive diethyl ether, washing the precipitate with 0 deg.C methanol for several times, and vacuum drying to constant weight;
and 3, dissolving the precipitate in methanol, stirring in an ice bath, adding 0.15g of dichlorotetracarbonyl dirhodium simultaneously, continuing stirring for 1h, adding excessive diethyl ether for precipitation, and filtering to obtain the polymer ligand polymetallic cage-shaped catalyst.
7. Use of a polymer ligand polymetallic cage catalyst according to claim 1 or 6 for the carbonylation of methanol to acetic acid.
8. The application of claim 7, wherein the polymer ligand polymetallic cage catalyst, methanol and methyl iodide are added into a pressure kettle, after carbon monoxide is introduced, the pressure of the carbon monoxide is kept to be 3-4 MPa, the reaction temperature is 150-200 ℃, and acetic acid is obtained after stirring reaction, wherein the dosage of the polymer ligand polymetallic cage catalyst in the reaction system is calculated by rhodium, and the content of rhodium is 500-2000 PPm; the usage amount of the catalyst promoter methyl iodide in the reaction system is 0.2-5 mol/L.
9. Use of a polymeric ligand polymetallic cage catalyst according to claim 1 or 6 for the catalytic carbonylation of methyl acetate to acetic anhydride.
10. The application of the catalyst as claimed in claim 9, wherein the polymer ligand polymetallic cage catalyst, methyl acetate, methyl iodide and acetic acid solvent are added into a pressure kettle, carbon monoxide is introduced to replace air in the pressure kettle, carbon monoxide is continuously introduced and hydrogen is added, the reaction temperature is 170-200 ℃, acetic anhydride is obtained after stirring reaction, the dosage of the polymer ligand polymetallic cage catalyst in the reaction system is calculated by rhodium, and the content of rhodium is 600-1500 PPm; the usage amount of the cocatalyst methyl iodide in the reaction system is 0.2-5 mol/L; the pressure of the mixed gas of carbon monoxide and hydrogen is 3.5-4.5 MPa, wherein the volume content of the hydrogen in the mixed gas is 1-10%.
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WO2020034476A1 (en) * 2018-08-17 2020-02-20 中国科学院大连化学物理研究所 Porous organic cage ligand containing p and n and complex catalyst and application

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Publication number Priority date Publication date Assignee Title
CN1349854A (en) * 2000-10-24 2002-05-22 中国科学院化学研究所 Bimetallic catalyst with Rh and Li as copolymer ligand and its preparation
CN1517151A (en) * 2003-01-17 2004-08-04 中国科学院化学研究所 Copolymer ligand rhodium-lithium bimetal catalyst and its manufacturing method and application
CN1672791A (en) * 2004-03-25 2005-09-28 香港理工大学 Double active species catalyst and its application
CN102794198A (en) * 2012-07-16 2012-11-28 江苏索普（集团）有限公司 Preparation method of catalyst for synthesizing propionic acid by ethanol carbonylation, and application thereof
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