CN113117757B - Bulk phase catalyst for synthesizing phenylpropionic acid and preparation and process thereof - Google Patents

Bulk phase catalyst for synthesizing phenylpropionic acid and preparation and process thereof Download PDF

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CN113117757B
CN113117757B CN201911418142.9A CN201911418142A CN113117757B CN 113117757 B CN113117757 B CN 113117757B CN 201911418142 A CN201911418142 A CN 201911418142A CN 113117757 B CN113117757 B CN 113117757B
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molecular sieve
catalyst
carbonate
modified
hydrotalcite
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CN113117757A (en
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张志智
王陶
孙潇磊
韩照明
刘全杰
张喜文
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/17—Silver

Abstract

The invention discloses a bulk phase catalyst for synthesizing phenylpropanoic acid. The catalyst comprises modified hydrotalcite, a modified molecular sieve, resin and active metal salt; the charge balancing anion of the modified hydrotalcite is carbonate; the modified molecular sieve is a cation modified molecular sieve, and the cation is selected from at least one of lithium, sodium, potassium and cesium ions; the active metal salt is at least one selected from metal salts AgI, agBr, agCl, cuI, cuBr and CuCl. The carbonate and the alkali metal cations are effectively separated and respectively fixed with the loaded solid, and the carbonate and the alkali metal salts are respectively the balance charges of the hydrotalcite and the molecular sieve and are connected with solid particle materials by chemical bonds, so that the loss of an active center and an alkali assistant can be effectively avoided in the reaction. The invention improves the performance and the service life of the catalyst and reduces the production cost.

Description

Bulk phase catalyst for synthesizing phenylpropionic acid and preparation and process thereof
Technical Field
The invention relates to a molded catalyst for synthesizing phenylpropanoic acid and a preparation method and a process thereof. In particular to a molded catalystReacting phenylacetylene with CO 2 A method for preparing phenylpropionic acid by carboxylation.
Background
Phenylpropargyl acid is an important synthetic intermediate. Can synthesize heterocyclic compounds such as coumarin, flavone, etc.; the substituted alkyne and other photoelectric materials can be prepared through decarboxylation cross-coupling reaction. In the prior art, the method for synthesizing the phenylpropanoid compounds is mainly oxidation and carboxylation reaction of phenylacetylene, the raw materials are formaldehyde or carbon monoxide and phenylacetylene, but the formaldehyde is expensive and the carbon monoxide has high toxicity, and the prior art has the defects of inconvenient operation and the like, so the application of the method is limited. The development of a new synthetic method of the phenylpropanoid compound has good application prospect.
The carboxylation of terminal alkyne and carbon dioxide can synthesize phenylpropanoic acid. The reaction can be carried out without a catalyst, but requires high reaction temperature and CO 2 Partial pressure. Matthias Arndt et al used 4, 7-diphenyl-1, 10-phenanthroline [ bis (tris 4-fluorophenyl) phosphine)]Cu (I) and cesium carbonate catalyze and synthesize phenylpropanoic acid at low temperature. Lu et al also synthesized phenylpropanoic acid at low temperatures using AgI as a catalyst. Compared with the copper (I) catalyst, the silver catalyst is more stable and higher in activity, and the using amount of the catalyst can be greatly reduced. The complex ligand can obviously improve the catalytic performance of cuprous and silver. The copper polyazacyclo-carbene catalyst and the silver polyazacyclo-carbene catalyst catalyze and synthesize the phenylpropanoic acid in the presence of cesium carbonate and under mild reaction conditions, and the catalysis system has high activity and stability and high yield in reaction.
The existing reaction process is carried out in a synthesis kettle, the used catalyst has high separation energy consumption, difficult separation and reuse, high catalyst reuse loss rate and short service life, and the reaction economy is seriously restricted. The fixed bed has significant advantages over the reaction kettle. And needs to develop a high-efficiency, green, cheap and easily available molded catalyst which is convenient to separate and reuse. Increasing the density of effective active sites in the shaped catalyst is an important aspect of high activity catalysts.
Disclosure of Invention
The present invention is directed to solve the above problems, and an object of the present invention is to provide a bulk phase catalyst and a method for preparing the same, by which carbon dioxide and phenylacetylene can be converted into phenylpropanoic acid under relatively mild reaction conditions.
The invention provides a bulk phase catalyst for synthesizing phenylpropanoic acid.
A bulk phase catalyst for synthesizing phenylpropanoic acid comprises modified hydrotalcite, modified molecular sieve, resin and active metal salt; the charge balancing anion of the modified hydrotalcite is carbonate; the modified molecular sieve is a cation modified molecular sieve, and cations are selected from at least one of lithium, sodium, potassium and cesium ions; the active metal salt is at least one selected from metal salts AgI, agBr, agCl, cuI, cuBr and CuCl.
Further, based on the weight of the catalyst, the content of the modified hydrotalcite is 9-22 wt%, the content of the modified molecular sieve is 11-32 wt%, the content of the active metal salt is 27-44 wt%, and the balance is resin.
Further, the weight ratio of the modified hydrotalcite to the modified molecular sieve is generally 1 to 4.
The second aspect of the invention also provides a preparation method of the bulk phase catalyst.
A preparation method of a bulk phase catalyst for synthesizing phenylpropionic acid comprises the following steps:
(1) Treating hydrotalcite with a carbonate solution, washing, drying and roasting to obtain modified hydrotalcite;
(2) Treating the molecular sieve with a salt solution containing metal cations, and washing, drying and roasting to obtain a modified molecular sieve;
(3) Crushing and mixing the modified hydrotalcite prepared in the step (1), the modified molecular sieve prepared in the step (2), the active metal salt, the phenolic resin and the urotropine together to prepare powder, and tabletting to prepare an active precursor;
(4) And heating the active precursor B under the protection of nitrogen at 120-200 ℃ for a period of time to obtain a bulk phase catalyst product.
In the invention, the hydrotalcite in the step (1) is commercial hydrotalcite. The hydrotalcite generally has a Mg/Al molar ratio of 3 to 6 and a specific surface area of 200 to 350m 2 (iv) g. The charge-balancing anion of the resulting modified hydrotalcite is carbonate (ion).
In the step (1), the carbonate is at least one selected from the group consisting of potassium carbonate, lithium carbonate, sodium carbonate and cesium carbonate. The treatment is generally carried out by dipping. And (2) modifying the hydrotalcite obtained in the step (1) by using carbonate ions contained in a soluble carbonate solution through impregnation, and replacing other anion impurities in the middle of the hydrotalcite sheet layered structure to further increase the carbonate ion content in the hydrotalcite. The carbonate solution has a concentration of 0.1 to 1mol/L in terms of carbonate ions. The solid-liquid ratio of the treatment is 1: 5-1. The treatment temperature is 25-70 ℃, the treatment time is 2-12 h, and the treatment times are generally 1-3. Each treatment operation includes impregnation followed by washing, drying and calcination. The roasting in the step (1) is carried out in a conventional atmosphere or in a vacuum state or in an inert atmosphere, the roasting temperature is 300-400 ℃, and the roasting time is 1-24 hours.
The molecular sieve in the step (2) is selected from Y-type molecular sieve, beta molecular sieve and ZSM-5 molecular sieve, and preferably at least one of Y molecular sieve, beta molecular sieve and ZSM-5 molecular sieve which are treated by acid and alkali. The cation is at least one of lithium, sodium, potassium and cesium.
The treatment in the step (2) adopts a dipping mode. The metal is selected from at least one of lithium, sodium, potassium and cesium, and is preferably cesium metal. The salt is at least one selected from the group consisting of halide salts, nitrate salts, carbonate salts, phosphate salts, and the like of the above metals. The concentration of the salt solution is 0.1-1 mol/L calculated by metal cations, and the solid-liquid ratio of the treatment is 1: 5-1. The treatment time is 2-12 h, the treatment temperature is 25-80 ℃, and the treatment times are 1-3. Each treatment operation includes impregnation followed by washing, drying and calcination.
The roasting in the step (2) is carried out in a conventional atmosphere or in a vacuum state or in an inert atmosphere, the roasting temperature is 400-600 ℃, and the roasting time is 1-12 hours.
In the step (3), the phenolic resin is thermoplastic phenolic resin, the softening point of the phenolic resin is 70-110 ℃, and the mass content of free phenol is 1-4%. The active metal salt is at least one selected from AgI, agBr, agCl, cuI, cuBr and CuCl. The mixing weight ratio of the hydrotalcite, the modified molecular sieve, the active metal salt, the phenolic resin and the urotropine is generally 1 (0.5-4): (2-4): (1 to 3.5): (0.1 to 0.35). The pressure for tabletting is generally 10 to 20 MPa, and the pressure is kept for a period of time, such as 2 to 5 minutes.
In the step (4), the active precursor B is heated at 120 to 200 ℃ under the protection of nitrogen, and the heating time is generally 0.5 to 4 hours. By heating, the thermoplastic phenolic resin and the urotropine react under the catalysis of other components, so that the thermoplastic phenolic resin is subjected to a curing reaction, gas is released at the same time, and pores are formed in a catalyst. After the catalyst is completely molded, a porous bulk catalyst is obtained.
In a third aspect of the invention there is also provided a process for the synthesis of phenylpropanoic acid wherein the catalyst used is a bulk catalyst as hereinbefore described.
The process comprises the following steps: the phenylacetylene and the dimethylformamide are mixed and then used as a liquid path, and flow through a fixed bed reactor containing a catalyst in a cocurrent or countercurrent manner with carbon dioxide gas to carry out carboxylation reaction under the carboxylation condition.
Further, the carboxylation conditions are as follows: the molar ratio of the dimethyl formamide to the phenylacetylene is 3-9, and the reaction pressure (namely CO) 2 Pressure) is 1-2 MPa, and the hourly space velocity of phenylacetylene liquid is 1-4 h -1 The reaction temperature is 60-80 ℃, and the gas-liquid (CO) is 2 Phenylacetylene) in a molar ratio of 2 to 5.
According to the method, the hydrotalcite is modified by using the salt solution containing carbonate ions, and other anion impurities in the layered structure of the hydrotalcite can be replaced by using the carbonate ions, so that the carbonate ion content in the hydrotalcite is increased. The molecular sieve is modified by soluble salt containing assistant ions, so that the assistant metal ions can be loaded on the surface and the inner pore canal of the molecular sieve, and then the assistant metal ions are firmly solidified on the molecular sieve by roasting. Therefore, the obtained catalyst for synthesizing the phenylpropanoic acid has the characteristic that the catalyst and the auxiliary agent are not easy to run off, the service life of the catalyst can be prolonged, and the utilization rate of the catalyst is greatly improved.
The phenolic resin used in the present invention can form a complex with an active metal salt by an amino group contained in the phenolic resin, in addition to being used as a molding agent, and can improve the nonionic property of the active metal and the catalytic activity of the active metal salt.
Compared with the prior art, the bulk phase catalyst and the process for synthesizing the phenylpropanoic acid have the following characteristics:
1. the catalyst of the invention effectively separates carbonate and alkali metal cations, and the carbonate and the alkali metal cations are respectively fixed with the loaded solid, and the carbonate and the alkali metal salts are respectively balance charges of hydrotalcite and a molecular sieve, and are connected with solid particle materials by chemical bonds. The chemical bond strength for charge balancing is large and difficult to lose. The loss of the active center and the alkali assistant can be effectively avoided in the reaction.
2. The catalyst has high content of active center and alkali assistant, and the active center and the alkali assistant can be effectively combined, so that the catalytic activity and the density of the effective active center are improved, the catalytic efficiency of the catalyst is improved, and the high space velocity reaction is realized.
3. The preparation method of the catalyst has simple process and no special environmental protection requirement; the active center of the catalyst is not easy to lose, the content of impurities in reaction products is reduced, the difficulty of post-treatment such as separation, refining and the like is reduced, and the generated waste is greatly reduced.
4. Compared with the existing catalyst and reaction process, the catalyst of the invention has continuous and stable reaction and low production cost. The reactants are easily separated from the catalyst. The heterogeneous catalyst composition and the reaction process prepared by the invention have the following characteristics: the catalyst has high activity, is relatively environment-friendly, generates less waste, and has simple production process and high product yield.
Detailed Description
The technical solution of the present invention will be further described with reference to the following specific examples.
All chemical reagents are analytically pure and are mainly purchased from Tianjin compounded chemical reagent, inc.;
NaY molecular sieve, having a silica to alumina ratio of 3, purchased from the chinese petrochemical catalyst division;
ZSM-5 molecular sieve with a silica-alumina ratio of 50 and purchased from catalyst works of southern Kai university;
hydrotalcite with Mg/Al molar ratio of 4.3 and specific surface area of 210 m 3 And/g, purchased from Beijing university of chemical industry.
The product analysis was performed by Agilent 7890A gas chromatography.
Example 1
(1) Preparing 0.2mol/L cesium carbonate solution, carrying out ion exchange on the cesium carbonate solution and hydrotalcite at a solid-liquid ratio of 1. Then filtered, washed and dried at 40 ℃. This was repeated once more. Finally, the mixture is roasted at 150 ℃ for 2 hours.
(2) Preparing a 1mol/L cesium chloride solution, carrying out ion exchange on the cesium chloride solution and a NaY molecular sieve at a solid-liquid ratio of 1. Then filtered, washed, dried at 40 ℃ and finally calcined at 550 ℃ for 2 hours. This was repeated once more.
(3) And (2) crushing and mixing 10g of the modified hydrotalcite obtained in the step (1), 20g of the ion exchange type molecular sieve obtained in the step (2), 20g of silver iodide, 20g of phenolic resin and 2g of urotropin, preparing powder, and sieving the powder by a 120-mesh sieve. Then, the mixture was tabletted and molded under a pressure of 14MPa for 4 minutes to obtain an active precursor B1.
(4) The activated precursor B1 was heated at 180 ℃ for 2 hours under nitrogen blanket. Then, the resulting mixture was pulverized into particles of 20 to 40 mesh to prepare a catalyst C1. The composition of catalyst C1 is shown in Table 1.
Example 2
(1) Preparing 0.2mol/L cesium carbonate solution, carrying out ion exchange on the cesium carbonate solution and hydrotalcite at a solid-liquid ratio of 1. Then filtered, washed and dried at 40 ℃. This was repeated once more. Finally, the mixture is roasted at 150 ℃ for 2 hours.
(2) Preparing a 1mol/L cesium chloride solution, carrying out ion exchange on the cesium chloride solution and a NaY molecular sieve at a solid-liquid ratio of 1. Then filtered, washed, dried at 40 ℃ and finally calcined at 550 ℃ for 2 hours. This was repeated once more.
(3) And (3) crushing and mixing 10g of the modified hydrotalcite obtained in the step (1), 5g of the ion exchange type molecular sieve obtained in the step (2), 20g of silver iodide, 10g of phenolic resin and 1g of urotropin, preparing powder, and sieving the powder by a 120-mesh sieve. Then, the mixture was tabletted and molded under a pressure of 14MPa for a holding time of 4 minutes to obtain an active precursor B2.
(4) The activated precursor B2 was heated at 180 ℃ for 2 hours under nitrogen blanket. Then, the mixture was pulverized into particles of 20 to 40 meshes to prepare a catalyst C2. The composition of catalyst C2 is shown in Table 1.
Example 3
(1) Preparing 0.2mol/L cesium carbonate solution, carrying out ion exchange on the cesium carbonate solution and hydrotalcite with a solid-to-liquid ratio of 1. Then filtered, washed and dried at 40 ℃. This was repeated once more. Finally, the mixture is roasted at 150 ℃ for 2 hours.
(2) Preparing a 1mol/L cesium chloride solution, carrying out ion exchange on the cesium chloride solution and a NaY molecular sieve at a solid-liquid ratio of 1. Then filtered, washed, dried at 40 ℃ and finally calcined at 550 ℃ for 2 hours. This was repeated once more.
(3) And (2) crushing and mixing 10g of the modified hydrotalcite obtained in the step (1), 40g of the ion exchange type molecular sieve obtained in the step (2), 40g of silver iodide, 35g of phenolic resin and 3.5g of urotropin, preparing powder, and sieving the powder by a 120-mesh sieve. Then, the mixture was tabletted and molded under a pressure of 14MPa for a holding time of 4 minutes to obtain an active precursor B3.
(4) The activated precursor B3 was heated at 180 ℃ for 2 hours under nitrogen blanket. Then, the resulting mixture was pulverized into particles of 20 to 40 mesh to prepare a catalyst C3. The composition of catalyst C3 is listed in table 1.
Example 4
(1) Preparing 0.2mol/L cesium carbonate solution, carrying out ion exchange on the cesium carbonate solution and hydrotalcite at a solid-liquid ratio of 1. Then filtered, washed and dried at 40 ℃. This was repeated once more. Finally, the mixture is roasted at 150 ℃ for 2 hours.
(2) Preparing a 1mol/L cesium chloride solution, carrying out ion exchange on the cesium chloride solution and a NaY molecular sieve at a solid-to-liquid ratio of 1. Then filtered, washed, dried at 40 ℃ and finally calcined at 550 ℃ for 2 hours. This was repeated once more.
(3) And (2) crushing and mixing 10g of the modified hydrotalcite obtained in the step (1), 10g of the ion exchange type molecular sieve obtained in the step (2), 20g of silver iodide, 10g of phenolic resin and 1g of urotropin, preparing powder, and sieving the powder by a 120-mesh sieve. Then, the mixture was tabletted and molded under a pressure of 14MPa for a holding time of 4 minutes to obtain an active precursor B4.
(4) The activated precursor B4 was heated at 180 ℃ for 2 hours under nitrogen blanket. Then, the mixture was pulverized into particles of 20 to 40 meshes to prepare a catalyst C4. The composition of catalyst C4 is given in Table 1.
Example 5
(1) Preparing 0.2mol/L cesium carbonate solution, carrying out ion exchange on the cesium carbonate solution and hydrotalcite at a solid-liquid ratio of 1. Then filtered, washed and dried at 40 ℃. This was repeated once more. Finally, the mixture is roasted for 2 hours at 150 ℃.
(2) Preparing a 1mol/L cesium chloride solution, carrying out ion exchange on the cesium chloride solution and a NaY molecular sieve at a solid-liquid ratio of 1. Then filtered, washed, dried at 40 ℃ and finally calcined at 550 ℃ for 2 hours. This was repeated once more.
(3) And (2) crushing and mixing 10g of the modified hydrotalcite obtained in the step (1), 30g of the ion exchange molecular sieve obtained in the step (2), 30g of cuprous iodide, 35g of phenolic resin and 3.5g of urotropin, preparing powder, and sieving the powder with a 120-mesh sieve. Then tabletting and forming are carried out, the pressure during tabletting is 14MPa, and the holding time is 4 minutes, thus obtaining the active precursor B5.
(4) The activated precursor B5 was heated at 180 ℃ for 2 hours under nitrogen. Then, the catalyst C5 was prepared by pulverizing the above-mentioned material into particles of 20 to 40 mesh. The composition of catalyst C5 is shown in Table 1.
TABLE 1 catalyst composition (unit, wt%)
Figure 18429DEST_PATH_IMAGE002
Examples 6 to 10
Bulk phase catalysts prepared in examples 1-5 were used to catalyze phenylacetylene with CO 2 The phenylpropionic acid is synthesized by reaction. In the fixed bed reactor, the mixture of phenylacetylene and dimethylformamide is in a liquid path, so that the phenylacetylene and the dimethylformamide simultaneously pass through a catalyst bed layer. After 144 hours of reaction, sampling was started and analysis was carried out by gas chromatography. The catalytic effect of the prepared catalyst is shown in table 2.
As can be seen from Table 2, the bulk catalyst of the present invention has excellent catalytic effect. The yield of the phenylpropanoic acid is 22-43%.
TABLE 2 Process conditions and results
Figure DEST_PATH_IMAGE003
Comparative example 1
Phenylacetylene 2.215g was dissolved in 100mL of dimethylformamide and charged into a 150mL autoclave. Adding 0.5g of silver iodide and 1g of cesium carbonate into a high-pressure reaction kettle, introducing CO 2 Exhausting the air in the reaction kettle, and introducing 1MPa of CO 2 Controlling the temperature of the gas at 70 ℃ and reacting for 24 hours. After the reaction, the mixture was cooled to room temperature, the catalyst was separated by filtration, and 100mL of Cs with a mass fraction of 12.14% was added to the separated mixture 2 CO 3 The solution was stirred at room temperature for 30 minutes, the mixture was washed with dichloromethane, the aqueous layer was retained, the aqueous layer was acidified with concentrated hydrochloric acid to pH =1 and then extracted with ether, and the organic layer was washed with dichloromethaneWater Mg 2 SO 4 Drying, filtering, rotary evaporating the liquid and vacuumizing to obtain a white solid with the yield of 29.9 percent.
Compared with the existing catalyst and reaction process, the catalyst and the reaction process thereof have the characteristics of high catalytic activity, no loss of active components and long service life.

Claims (19)

1. A bulk phase catalyst for synthesizing phenylpropanoic acid comprises modified hydrotalcite, modified molecular sieve, resin and active metal salt; the charge balancing anion of the modified hydrotalcite is carbonate; the modified molecular sieve is a cation modified molecular sieve, and cations are selected from at least one of lithium, sodium, potassium and cesium ions; the active metal salt is at least one selected from metal salts AgI, agBr, agCl, cuI, cuBr and CuCl.
2. A bulk catalyst according to claim 1, wherein the modified hydrotalcite is present in an amount of 9 to 22 wt%, the modified molecular sieve is present in an amount of 11 to 32 wt%, the active metal salt is present in an amount of 27 to 44 wt%, and the balance is resin, based on the weight of the catalyst.
3. The bulk catalyst according to claim 1 or 2, wherein the weight ratio of the modified hydrotalcite to the modified molecular sieve is 1 to 4 to 2.
4. A process for the preparation of a bulk catalyst for the synthesis of phenylpropanoic acid as claimed in any one of claims 1 to 3, comprising:
(1) Treating hydrotalcite with a carbonate solution, washing, drying and roasting to obtain modified hydrotalcite;
(2) Treating the molecular sieve with a salt solution containing metal cations, and washing, drying and roasting to obtain a modified molecular sieve;
(3) Crushing and mixing the modified hydrotalcite prepared in the step (1), the modified molecular sieve prepared in the step (2), the active metal salt, the phenolic resin and the urotropine together to prepare powder, and tabletting to prepare an active precursor B;
(4) And heating the active precursor B under the protection of nitrogen at 120-200 ℃ for a period of time to obtain a bulk phase catalyst.
5. The process according to claim 4, wherein said hydrotalcite has a Mg/Al molar ratio of 3 to 6 and a specific surface area of 200 to 350m 2 /g。
6. The method according to claim 4, wherein the carbonate is at least one selected from the group consisting of potassium carbonate, lithium carbonate, sodium carbonate and cesium carbonate.
7. The method according to claim 4 or 6, wherein the carbonate solution has a concentration of 0.1 to 1mol/L in terms of carbonate ions.
8. The method according to claim 4, wherein the solid-to-liquid ratio of the treatment in the step (1) is 1: 5-1 g/L, the treatment temperature is 25-70 ℃, the treatment time is 2-12 h, and the treatment times are 1-3 times.
9. The preparation method according to claim 4, wherein the roasting temperature in the step (1) is 300-400 ℃, and the roasting time is 1-24 h.
10. The method of claim 4, wherein the molecular sieve is at least one selected from the group consisting of a Y-type molecular sieve, a beta molecular sieve and a ZSM-5 molecular sieve.
11. The method according to claim 4, wherein the metal in the step (2) is at least one selected from the group consisting of lithium, sodium, potassium and cesium.
12. The method according to claim 11, wherein the salt in the step (2) is at least one selected from the group consisting of a halide salt, a nitrate salt, a carbonate salt and a phosphate salt of a metal, and the concentration of the salt solution is 0.1 to 1mol/L in terms of metal cation.
13. The method according to claim 4, wherein the solid-to-liquid ratio of the treatment in the step (2) is 1: 5-1 g/L, the treatment time is 2-12 h, the treatment temperature is 25-80 ℃, and the treatment times are 1-3.
14. The preparation method according to claim 4, wherein the roasting temperature in the step (2) is 400-600 ℃, and the roasting time is 1-12 h.
15. The method according to claim 4, wherein the phenolic resin is a thermoplastic phenolic resin, and the softening point of the thermoplastic phenolic resin is 70 to 110 ℃, and the mass content of the free phenol is 1 to 4 percent.
16. The method according to claim 4, wherein the active metal salt is at least one selected from the group consisting of AgI, agBr, agCl, cuI, cuBr, and CuCl.
17. The method according to claim 4, wherein the heating in step (4) is carried out for 0.5 to 4 hours.
18. A process for synthesizing phenylpropanoic acid, comprising: mixing phenylacetylene and dimethylformamide to serve as a liquid path, enabling the mixture and carbon dioxide gas to pass through a fixed bed reactor containing a catalyst in a cocurrent or countercurrent manner, and performing carboxylation reaction under the carboxylation condition; the catalyst is a bulk catalyst according to any one of claims 1 to 3.
19. The process of claim 18, wherein said carboxylation conditions are: the mol ratio of the dimethyl formamide to the phenylacetylene is 3-9, the reaction pressure is 1-2 MPa, and the volume space velocity of the phenylacetylene liquid is 1-4 h -1 Reaction temperatureThe temperature is between 60 and 80 ℃, and CO 2 The mol ratio of phenylacetylene is 2-5.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1060294A1 (en) * 1998-03-05 2000-12-20 Forschungszentrum Karlsruhe GmbH Method for carboxylating terminal alkynes
CN1307554A (en) * 1998-05-15 2001-08-08 研究三角协会 Method of preparing alkyl carboxylic acid by carboxylation of lower alkanes methane
WO2013110998A1 (en) * 2012-01-25 2013-08-01 Council Of Scientific & Industrial Research (An Indian Registered Body Incorporated Under The Registration Of Societies Act (Act Xxi Of 1860) A process for preparation of alkynyl carboxylic acids
CN104117390A (en) * 2014-06-20 2014-10-29 南开大学 Preparation method of silver nano particle loaded metal organic framework complex catalyst
CN108404983A (en) * 2018-03-23 2018-08-17 华东师范大学 A kind of preparation and its application of ordered mesoporous phenolic resin Polymer-supported silver catalyst
CN108607603A (en) * 2016-12-09 2018-10-02 中国科学院大连化学物理研究所 A kind of CO2Synthesize acetylenic acid catalyst and its preparation and application

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6951830B2 (en) * 2003-08-05 2005-10-04 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst compositions, their production and use in conversion processes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1060294A1 (en) * 1998-03-05 2000-12-20 Forschungszentrum Karlsruhe GmbH Method for carboxylating terminal alkynes
CN1307554A (en) * 1998-05-15 2001-08-08 研究三角协会 Method of preparing alkyl carboxylic acid by carboxylation of lower alkanes methane
WO2013110998A1 (en) * 2012-01-25 2013-08-01 Council Of Scientific & Industrial Research (An Indian Registered Body Incorporated Under The Registration Of Societies Act (Act Xxi Of 1860) A process for preparation of alkynyl carboxylic acids
CN104117390A (en) * 2014-06-20 2014-10-29 南开大学 Preparation method of silver nano particle loaded metal organic framework complex catalyst
CN108607603A (en) * 2016-12-09 2018-10-02 中国科学院大连化学物理研究所 A kind of CO2Synthesize acetylenic acid catalyst and its preparation and application
CN108404983A (en) * 2018-03-23 2018-08-17 华东师范大学 A kind of preparation and its application of ordered mesoporous phenolic resin Polymer-supported silver catalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Finashina E D等.Carboxylation of phenylacetylene by carbon dioxide on heterogeneous Ag-containing catalysis.《Russian Chemical Bulletin》.2014,第第63卷卷(第第63卷期),全文. *
董冬吟等.二氧化碳参与的有机化学反应.《化学进展》.2009,(第undefined期),全文. *

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