Use of a stabilizer in cobalt-catalyzed hydroformylation reactions
By using a compound with an o-phenylenediamine structure as a stabilizer in combination with a cobalt catalyst, the problems of easy deactivation of cobalt catalyst and high cost of phosphine ligands are solved, enabling stable recycling of cobalt catalyst and cost reduction.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-10
- Publication Date
- 2026-03-24
AI Technical Summary
In existing cobalt-catalyzed hydroformylation reactions, the catalyst is prone to deactivation, and phosphine ligands are costly and easily oxidized, making it difficult to achieve stable recycling.
A compound containing an o-phenylenediamine structure is used as a stabilizer in conjunction with a cobalt catalyst to catalyze the hydroformylation reaction of olefins with syngas, maintaining the catalyst in a homogeneous state and facilitating recycling.
This approach improves the stability and economic efficiency of cobalt catalysts, avoids precipitation formation, facilitates direct distillation separation, and reduces catalyst costs.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of homogeneous catalysis, and more particularly to the application of a stabilizer in cobalt-catalyzed hydroformylation reactions. Background Technology
[0002] Cobalt-catalyzed hydroformylation is a highly efficient method for converting olefins and syngas, and is an important means of synthesizing aldehydes and alcohols, achieving 100% atom economy. Since the discovery of hydroformylation in 1938, the first-generation hydroformylation process used unmodified cobalt carbonyl as a catalyst under high temperature and pressure. The recognized active species of unmodified cobalt carbonyl catalysts is HCo(CO)3, which is generated by the dissociation of a CO molecule from HCo(CO)4. A large amount of volatile HCo(CO)4 is present in the reaction system. This compound gradually decomposes upon leaving the high-pressure CO atmosphere, forming a precipitate and losing its catalytic activity. Subsequent processes improved the cobalt separation and recovery method by adding an alkaline aqueous solution to the hydroformylation reaction mixture, converting HCo(CO)4 into water-soluble [Co(CO)4]. - After phase separation, the [Co(CO)4]-rich [Co(CO)4]- - The aqueous phase is acidified with sulfuric acid in the presence of H2 / CO to regenerate [Co(H)(CO)4], which is then extracted from the olefins and reintroduced into the hydroformylation reaction (Exxon process). This process avoids deactivation of the cobalt catalyst and allows for recycling after separation, but it requires the extraction of the cobalt catalyst using alkali and acid under a CO atmosphere.
[0003] The second-generation process uses a Co catalytic system modified with phosphine ligands. While this reduces catalyst activity, it improves regioselectivity and, more importantly, allows for catalyst recycling. The phosphine ligands protect the cobalt catalyst center, ensuring the cobalt catalyst remains homogeneous and does not precipitate even in the absence of a CO atmosphere. After distillation to separate aldehydes and alcohols, the cobalt catalyst can be reintroduced into the reactor to catalyze the hydroformylation of olefins. However, phosphine ligands are expensive, easily oxidized in air, and highly toxic. Summary of the Invention
[0004] The technical problem to be solved by the present invention is to provide a low-cost and stable stabilizer for use in cobalt-catalyzed hydroformylation reaction.
[0005] To address the aforementioned problems, the present invention provides an application of a stabilizer in cobalt-catalyzed hydroformylation, characterized in that: a compound containing an o-phenylenediamine structure is used as a stabilizer for the cobalt catalyst, and the stabilizer is used in conjunction with the cobalt catalyst to catalyze the hydroformylation reaction of olefins and syngas, thereby achieving the recycling of the cobalt catalyst.
[0006] The stabilizer has the structure shown in general formula (I) or general formula (II):
[0007]
[0008] In the formula: R 1 R 2 It is one of alkyl, aryl, or hydrogen atoms, and R 1 R 2 Same or different; R 3 R 4 It is one of alkyl, aryl, or hydrogen atoms, and R 3 R 4 Same or different.
[0009] The molar concentrations of both the stabilizer and the cobalt catalyst are 1 to 10 mmol / L.
[0010] The cobalt catalyst is selected from one of the following: cobalt octacarbonyl, sodium cobalt carbonyl, cobalt acetate, cobalt acetylacetonate, cobalt isooctanoate, and cobalt naphthenate.
[0011] The olefin is selected from one of pentene, hexene, octene, diisobutylene, dodecene, styrene, and butadiene.
[0012] The synthesis gas is a mixture of carbon monoxide and hydrogen, with a pressure of 4~10 MPa, wherein the volume ratio of carbon monoxide to hydrogen is 1:2~2:1.
[0013] The hydroformylation reaction is carried out at a temperature of 100-190 degrees Celsius for 1-24 hours.
[0014] The solvent for the hydroformylation reaction is selected from one of toluene, xylene, benzene, methyl tert-butyl ether, 1,4-dioxane, and tetrahydrofuran.
[0015] Compared with the prior art, the present invention has the following advantages:
[0016] 1. This invention uses a compound containing an o-phenylenediamine structure as a stabilizer, which can prevent the cobalt catalyst from precipitating after the reaction, so that the catalyst always remains homogeneous in the reaction system, which is convenient for direct distillation separation and can be directly recycled.
[0017] 2. This invention uses a compound containing an o-phenylenediamine structure as a stabilizer, which avoids the use of expensive and easily oxidized phosphine ligands. It has the advantages of low price, low toxicity and stability in air, which can greatly improve the stability of the reaction system and reduce the cost of catalyst. Detailed Implementation
[0018] Application of a stabilizer in cobalt-catalyzed hydroformylation reaction: A compound containing an o-phenylenediamine structure is used as a stabilizer for the cobalt catalyst. This stabilizer is used in conjunction with the cobalt catalyst to catalyze the hydroformylation reaction of olefins and syngas at a temperature of 100-190 degrees Celsius for 1-24 hours, thereby achieving the recycling of the cobalt catalyst.
[0019] Wherein: the stabilizer has the structure shown in general formula (I) or general formula (II):
[0020]
[0021] In the formula: R 1 R 2 It is one of alkyl, aryl, or hydrogen atoms, and R 1 R 2 Same or different; R 3 R 4 It is one of alkyl, aryl, or hydrogen atoms, and R 3 R 4 Same or different.
[0022] The molar concentrations of both the stabilizer and the cobalt catalyst were 1–10 mmol / L.
[0023] The cobalt catalyst is selected from one of the following: cobalt octacarbonyl, sodium cobalt carbonyl, cobalt acetate, cobalt acetylacetonate, cobalt isooctanoate, and cobalt naphthenate.
[0024] The olefin is selected from one of pentene, hexene, octene, diisobutylene, dodecene, styrene, and butadiene.
[0025] Syngas is a mixture of carbon monoxide and hydrogen, with a pressure of 4~10 MPa, and the volume ratio (L / L) of carbon monoxide to hydrogen is 1:2~2:1.
[0026] The solvent for the hydroformylation reaction is selected from one of toluene, xylene, benzene, methyl tert-butyl ether, 1,4-dioxane, and tetrahydrofuran.
[0027] The specific process is as follows:
[0028] An olefin and organic solvent were added to the reactor at a molar concentration (mmol / L), and stirred until a solution was formed. Then, 1–10 parts of cobalt catalyst and 1–10 parts of a compound containing an o-phenylenediamine structure were added to a unit volume of the solution, and the reactor was sealed. After purging the reactor with inert gas, 4–10 MPa of syngas (carbon monoxide to hydrogen in a ratio of 1:2 to 2:1) was introduced, and the reactor was heated to 100–190 degrees Celsius for 1–24 hours. Afterward, the reactor was cooled to room temperature, the gas was slowly released, the reactor was opened, a liquid sample was taken, diluted, and analyzed by gas chromatography.
[0029] When recycling the catalyst, the mixture after the above reaction is distilled under reduced pressure, and the distillation residue is added back to the reactor. A unit volume of olefin solution is then added, and the reactor is sealed. After the air in the reactor is purged with inert gas, syngas is introduced again, and the reactor is heated to the reaction temperature. After the reaction is completed, samples are taken for analysis.
[0030] Example 1
[0031] 40 mL of 1-octene and 160 mL of toluene were added to a 500 mL reactor and stirred until a solution was formed. 0.5 mmol of cobalt octacarbonyl and 1 mmol of o-phenylenediamine were then added to the solution, and the reactor was sealed. After purging the reactor with inert gas, a syngas mixture of carbon monoxide and hydrogen in a 1:1 ratio was introduced at 6 MPa. The reactor was heated to 140°C and reacted for 4 hours. After cooling to room temperature, the gas was slowly released, the reactor was opened, and a liquid sample was taken. After dilution, gas chromatography analysis showed an olefin conversion of 96% and a total yield of nonanal and nonanol of 87%. Furthermore, no precipitation occurred when the mixture was placed in air after the reaction.
[0032] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 100°C. The distillation residue was mixed with 40 mL of 1-octene and 160 mL of toluene, and added to a reaction vessel, which was then sealed. After purging the vessel with inert gas, synthesis gas with a carbon monoxide and hydrogen ratio of 1:1 was introduced at 6 MPa. The mixture was heated to 140°C and reacted for 4 hours, then cooled to room temperature. Sampling analysis showed an olefin conversion of 95% and a total yield of 88% for nonanal and nonanol.
[0033] Comparative Example
[0034] 40 mL of 1-octene and 160 mL of toluene were added to a 500 mL reactor and stirred until a solution was formed. 0.5 mmol of cobalt octacarbonyl was added to the solution, and the reactor was sealed. After purging the reactor with inert gas, a syngas mixture of carbon monoxide and hydrogen in a 1:1 ratio was introduced at 6 MPa. The reactor was heated to 140°C and reacted for 4 hours. After cooling to room temperature, the gas was slowly released, the reactor was opened, and a liquid sample was taken. After dilution, gas chromatography analysis showed an olefin conversion of 96% and a total yield of nonanal and nonanol of 87%. When the reaction mixture was left in air, a large amount of pink precipitate appeared.
[0035] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 100°C. The distillation residue was mixed with 40 mL of 1-octene and 160 mL of toluene, and added to a reaction vessel, which was then sealed. After purging the vessel with inert gas, syngas in a 1:1 ratio of carbon monoxide and hydrogen was introduced at 6 MPa. The mixture was heated to 140°C and reacted for 4 hours, then cooled to room temperature. Sampling analysis showed an olefin conversion of 45% and a total yield of 19% for nonanal and nonanol.
[0036] Example 2
[0037] Add 40 mL of 1-pentene and 160 mL of benzene to a 500 mL reactor and stir until a solution is formed. Then add 2 mmol of cobalt acetate and 2 mmol of N,N'-dimethyl-o-phenylenediamine (formula I,R) to the solution. 1 =Hydrogen atom, R 2 =Methyl), a sealed reaction vessel. After purging the air from the vessel with inert gas, syngas with a carbon monoxide and hydrogen ratio of 1:1 at 4 MPa was introduced, heated to 100 degrees Celsius, and reacted for 24 hours. The mixture was then cooled to room temperature, the gas was slowly released, the reaction vessel was opened, and a liquid sample was taken. After dilution, gas chromatography analysis showed an olefin conversion of 99% and a total yield of hexanal and hexanol of 92%. Furthermore, no precipitation occurred when the reaction mixture was placed in air.
[0038] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 60°C. The distillation residue was mixed with 40 mL of 1-pentene and 160 mL of benzene, and added to a reaction vessel, which was then sealed. After purging the vessel with inert gas, syngas in a 1:1 ratio of carbon monoxide and hydrogen was introduced at 4 MPa. The mixture was heated to 100°C and reacted for 24 hours, then cooled to room temperature. Sampling analysis showed an olefin conversion of 99% and a total yield of 90% for hexanal and hexanol.
[0039] Example 3
[0040] Add 40 mL of 1-hexene and 160 mL of methyl tert-butyl ether to a 500 mL reactor, stir until homogeneous to form a solution, and then add 0.2 mmol of cobalt acetylacetonate and 0.2 mmol of 2-phenylbenzimidazole (formula II, R) to the solution. 3 =Hydrogen atom, R 4 =phenyl), a sealed reaction vessel. After purging the air from the vessel with inert gas, syngas with a carbon monoxide and hydrogen ratio of 2:1 at 10 MPa was introduced, heated to 150 degrees Celsius, and reacted for 12 hours. The mixture was then cooled to room temperature, the gas was slowly released, the reaction vessel was opened, and a liquid sample was taken. After dilution, gas chromatography analysis showed an olefin conversion of 99% and a total yield of 91% for heptanal and heptanol. Furthermore, no precipitation occurred when the reaction mixture was placed in air.
[0041] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 60°C. The distillation residue was mixed with 40 mL of 1-hexene and 160 mL of methyl tert-butyl ether and added to a reaction vessel, which was then sealed. After purging the vessel with inert gas, syngas with a carbon monoxide and hydrogen ratio of 2:1 at 10 MPa was introduced. The mixture was heated to 150°C and reacted for 12 hours, then cooled to room temperature. Sampling analysis showed an olefin conversion of 99% and a total yield of 93% for heptanal and heptanol.
[0042] Example 4
[0043] Add 40 mL of diisobutylene and 160 mL of 1,4-dioxane to a 500 mL reactor, stir until a solution is formed, and then add 0.5 mmol of cobalt isooctanoate and 0.5 mmol of N-methyl-2-phenylbenzimidazole (formula II, R) to the solution. 3 =Methyl, R 4 =phenyl), a sealed reaction vessel. After purging the air from the vessel with inert gas, syngas with a carbon monoxide and hydrogen ratio of 1:2 at 6 MPa was introduced, heated to 170 degrees Celsius, and reacted for 1 hour. The mixture was then cooled to room temperature, the gas was slowly released, the reaction vessel was opened, and a liquid sample was taken. After dilution, gas chromatography analysis showed an olefin conversion rate of 88% and a total yield of 67% for isononanal and isononyl alcohol. Furthermore, no precipitation occurred when the reaction mixture was placed in air.
[0044] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 100°C. The distillation residue was mixed with 40 mL of diisobutylene and 160 mL of 1,4-dioxane, and added to a reaction vessel, which was then sealed. After purging the vessel with inert gas, syngas with a carbon monoxide and hydrogen ratio of 1:2 at 6 MPa was introduced. The mixture was heated to 170°C and reacted for 1 hour, then cooled to room temperature. Sampling analysis showed an olefin conversion of 90% and a total yield of 65% for isononanal and isononanol.
[0045] Example 5
[0046] Add 40 mL of dodecene and 160 mL of xylene to a 500 mL reactor and stir until a solution is formed. Then add 1 mmol of cobalt naphthenate and 1 mmol of N-butyl-2-butylbenzimidazole (formula II, R) to the solution. 3 =Butyl, R 4=Butyl), a closed reaction vessel. After purging the air from the vessel with inert gas, syngas with a carbon monoxide and hydrogen ratio of 1:1 at 6 MPa was introduced, heated to 190 degrees Celsius, and reacted for 1 hour. The mixture was then cooled to room temperature, the gas was slowly released, the reaction vessel was opened, and a liquid sample was taken. After dilution, gas chromatography analysis showed an olefin conversion of 78% and a total yield of 73% for tridecanal and tridecanol. Furthermore, no precipitation occurred when the reaction mixture was placed in air.
[0047] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 120°C. The distillation residue was mixed with 40 mL of dodecene and 160 mL of xylene, and added to a reaction vessel, which was then sealed. After purging the vessel with inert gas, syngas in a 1:1 ratio of carbon monoxide and hydrogen was introduced at 6 MPa. The mixture was heated to 190°C and reacted for 1 hour, then cooled to room temperature. Sampling analysis showed an olefin conversion of 79% and a total yield of 68% for tridecanal and tridecanol.
[0048] Example 6
[0049] Add 20 mL of styrene and 180 mL of tetrahydrofuran to a 500 mL reactor, stir until homogeneous to form a solution, and then add 1 mmol of sodium cobalt carbonyl and 1 mmol of N,N'-diphenyl-o-phenylenediamine (general formula I, R) to the solution. 1 =Hydrogen atom, R 2 =phenyl), a sealed reaction vessel. After purging the air from the vessel with inert gas, synthesis gas with a carbon monoxide and hydrogen ratio of 1:1 was introduced at 6 MPa. The mixture was heated to 100 degrees Celsius and reacted for 24 hours. After cooling to room temperature, the gas was slowly released, the reaction vessel was opened, and a liquid sample was taken. After dilution, gas chromatography analysis showed that the olefin conversion rate was 99%, and the total yield of phenylacetaldehyde and phenylethanol was 52%. Furthermore, no precipitation occurred when the mixture was placed in air after the reaction.
[0050] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 100°C. The distillation residue was mixed with 20 mL of styrene and 180 mL of tetrahydrofuran, and added to a reaction vessel, which was then sealed. After purging the vessel with inert gas, syngas with a carbon monoxide and hydrogen ratio of 1:1 was introduced at 6 MPa. The mixture was heated to 100°C and reacted for 24 hours, then cooled to room temperature. Sampling analysis showed an olefin conversion of 99% and a total yield of phenylpropanal and phenylpropanol of 50%.
[0051] Example 7
[0052] Add 200 mL of butadiene to a 500 mL reactor. Then add 1 mmol of sodium cobalt carbonyl and 1 mmol of N,N,N',N'-tetramethyl-o-phenylenediamine (general formula I, R) to the above solution. 1 = R2 =phenyl), a sealed reaction vessel. After purging the air from the vessel with inert gas, synthesis gas with a carbon monoxide and hydrogen ratio of 1:1 was introduced at 6 MPa. The mixture was heated to 120 degrees Celsius and reacted for 4 hours. Then, it was cooled to room temperature, the gas was slowly released, the reaction vessel was opened, and a liquid sample was taken. After dilution, gas chromatography analysis showed that the olefin conversion rate was 99%, and the total yield of aldehydes and alcohols was 72%. Furthermore, no precipitation occurred when the reaction mixture was placed in air.
[0053] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 80°C. The distillation residue was mixed with 20 mL of butadiene and 180 mL of tetrahydrofuran, and added to a reaction vessel, which was then sealed. After purging the vessel with inert gas, syngas with a carbon monoxide and hydrogen ratio of 1:1 was introduced at 6 MPa. The mixture was heated to 120°C and reacted for 4 hours, then cooled to room temperature. Sampling analysis showed an olefin conversion of 99% and a total yield of aldehydes and alcohols of 68%.
[0054] Example 8
[0055] Add 40 mL of 2-octene and 160 mL of methyl tert-butyl ether to a 500 mL reactor, stir until homogeneous to form a solution, and then add 0.5 mmol of cobalt acetate and 0.5 mmol of 2-phenylbenzimidazole (formula II, R) to the solution. 3 =Hydrogen atom, R 4 =phenyl), a sealed reaction vessel. After purging the air from the vessel with inert gas, synthesis gas with a carbon monoxide and hydrogen ratio of 1:1 was introduced at 6 MPa. The mixture was heated to 150 degrees Celsius and reacted for 6 hours. Then, it was cooled to room temperature, the gas was slowly released, the reaction vessel was opened, and a liquid sample was taken. After dilution, gas chromatography analysis showed an olefin conversion rate of 96% and a total yield of 78% for heptanal and heptanol. Furthermore, no precipitation occurred when the mixture was left in air after the reaction.
[0056] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 90°C. The distillation residue was mixed with 40 mL of 2-octene and 160 mL of methyl tert-butyl ether and added to a reaction vessel, which was then sealed. After purging the vessel with inert gas, synthesis gas with a carbon monoxide and hydrogen ratio of 1:1 was introduced at 6 MPa. The mixture was heated to 150°C and reacted for 6 hours, then cooled to room temperature. Sampling analysis showed an olefin conversion of 97% and a total yield of nonanal and nonanol of 76%.
[0057] Example 9
[0058] 40 mL of 2-hexene and 160 mL of tetrahydrofuran were added to a 500 mL reactor and stirred until a solution was formed. 0.5 mmol of cobalt acetate and 0.5 mmol of o-phenylenediamine were then added to the solution, and the reactor was sealed. After purging the reactor with inert gas, a syngas mixture of carbon monoxide and hydrogen in a 1:1 ratio (6 MPa) was introduced. The reactor was heated to 150°C and reacted for 6 hours. After cooling to room temperature, the gas was slowly released, the reactor was opened, and a liquid sample was taken. After dilution, gas chromatography analysis showed an olefin conversion of 96% and a total yield of 78% for heptanal and heptanol. No precipitation occurred when the mixture was left in air after the reaction.
[0059] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 60°C. The distillation residue was mixed with 40 mL of 2-hexene and 160 mL of tetrahydrofuran, and added to a reaction vessel, which was then sealed. After purging the air from the vessel with inert gas, syngas with a carbon monoxide and hydrogen ratio of 1:1 was introduced at 6 MPa. The mixture was heated to 150°C and reacted for 6 hours, then cooled to room temperature. Sampling analysis showed an olefin conversion of 97% and a total yield of 76% for heptanal and heptanol.
[0060] Example 10
[0061] Add 40 mL of cyclopentene and 160 mL of tetrahydrofuran to a 500 mL reactor, stir until homogeneous to form a solution, and then add 0.5 mmol of cobalt acetate and 0.5 mmol of 2-phenylbenzimidazole (formula II, R) to the solution. 3 =Hydrogen atom, R 4 =phenyl), a sealed reaction vessel. After purging the air from the vessel with inert gas, synthesis gas with a carbon monoxide and hydrogen ratio of 1:1 was introduced at 6 MPa. The mixture was heated to 120 degrees Celsius and reacted for 12 hours. After cooling to room temperature, the gas was slowly released, the reaction vessel was opened, and a liquid sample was taken. After dilution, gas chromatography analysis showed that the olefin conversion rate was 98%, and the total yield of hexanal and hexanol was 76%. Furthermore, no precipitation occurred when the reaction mixture was placed in air.
[0062] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 60°C. The distillation residue was mixed with 40 mL of cyclopentene and 160 mL of tetrahydrofuran, and added to a reaction vessel, which was then sealed. After purging the vessel with inert gas, syngas with a carbon monoxide and hydrogen ratio of 1:1 was introduced at 6 MPa. The mixture was heated to 120°C and reacted for 12 hours, then cooled to room temperature. Sampling analysis showed an olefin conversion of 98% and a total yield of 76% for hexanal and hexanol.
[0063] Example 11
[0064] 40 mL of cyclohexene and 160 mL of tetrahydrofuran were added to a 500 mL reactor and stirred until a solution was formed. 0.5 mmol of cobalt acetate and 0.5 mmol of o-phenylenediamine were then added to the solution, and the reactor was sealed. After purging the reactor with inert gas, syngas with a carbon monoxide to hydrogen ratio of 2:1 at 10 MPa was introduced. The reactor was heated to 100°C and reacted for 12 hours. After cooling to room temperature, the gas was slowly released, the reactor was opened, and a liquid sample was taken. After dilution, gas chromatography analysis showed an olefin conversion of 98% and a total yield of hexanal and hexanol of 89%. Furthermore, no precipitation occurred when the reaction mixture was placed in air.
[0065] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 70°C. The distillation residue was mixed with 40 mL of cyclohexene and 160 mL of tetrahydrofuran, and added to a reaction vessel, which was then sealed. After purging the vessel with inert gas, syngas with a carbon monoxide and hydrogen ratio of 2:1 at 10 MPa was introduced. The mixture was heated to 100°C and reacted for 12 hours, then cooled to room temperature. Sampling analysis showed an olefin conversion of 99% and a total yield of hexanal and hexanol of 86%.
[0066] Example 12
[0067] Add 40 mL of 1-hexene and 160 mL of methyl tert-butyl ether to a 500 mL reactor, stir until homogeneous to form a solution, and then add 0.5 mmol of cobalt acetate and 0.5 mmol of 2-phenylbenzimidazole (formula II, R) to the solution. 3 =Hydrogen atom, R 4 =phenyl), a sealed reaction vessel. After purging the air from the vessel with inert gas, synthesis gas with a carbon monoxide and hydrogen ratio of 1:1 was introduced at 6 MPa. The mixture was heated to 150 degrees Celsius and reacted for 6 hours. Then, it was cooled to room temperature, the gas was slowly released, the reaction vessel was opened, and a liquid sample was taken. After dilution, gas chromatography analysis showed an olefin conversion rate of 99% and a total yield of 88% for heptanal and heptanol. Furthermore, no precipitation occurred when the reaction mixture was placed in air.
[0068] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 60°C. The distillation residue was mixed with 40 mL of 1-hexene and 160 mL of methyl tert-butyl ether and added to a reaction vessel, which was then sealed. After purging the vessel with inert gas, syngas with a carbon monoxide and hydrogen ratio of 1:1 was introduced at 6 MPa. The mixture was heated to 150°C and reacted for 6 hours, then cooled to room temperature. The above operation was repeated 5 times after the reaction was restarted. The total conversion of olefins after 5 recycling cycles was 95%, and the total yield of heptanal and heptanol was 85%.
Claims
1. The application of a stabilizer in a cobalt-catalyzed hydroformylation reaction, characterized in that: A compound containing an o-phenylenediamine structure is used as a stabilizer for a cobalt catalyst. This stabilizer is used in conjunction with the cobalt catalyst to catalyze the hydroformylation reaction of olefins and syngas, thereby achieving the recycling of the cobalt catalyst. The stabilizer is one of o-phenylenediamine, N,N'-dimethylo-phenylenediamine, 2-phenylbenzimidazole, N-methyl-2-phenylbenzimidazole, N-butyl-2-butylbenzimidazole, N,N'-diphenylo-phenylenediamine, and N,N,N',N'-tetramethylo-phenylenediamine. The cobalt catalyst is selected from one of octacarbonyldicobalt, sodium carbonyl cobalt, cobalt acetate, cobalt acetylacetone, cobalt isooctanoate, and cobalt naphthenate.
2. The application of the stabilizer as described in claim 1 in the cobalt-catalyzed hydroformylation reaction, characterized in that: The molar concentrations of both the stabilizer and the cobalt catalyst are 1 to 10 mmol / L.
3. The application of the stabilizer as described in claim 1 in the cobalt-catalyzed hydroformylation reaction, characterized in that: The olefin is selected from one of pentene, hexene, octene, diisobutylene, dodecene, styrene, and butadiene.
4. The application of the stabilizer as described in claim 1 in the cobalt-catalyzed hydroformylation reaction, characterized in that: The synthesis gas is a mixture of carbon monoxide and hydrogen, with a pressure of 4~10 MPa, wherein the volume ratio of carbon monoxide to hydrogen is 1:2~2:
1.
5. The application of the stabilizer as described in claim 1 in the cobalt-catalyzed hydroformylation reaction, characterized in that: The hydroformylation reaction is carried out at a temperature of 100-190 degrees Celsius for 1-24 hours.
6. The application of the stabilizer as described in claim 1 in the cobalt-catalyzed hydroformylation reaction, characterized in that: The solvent for the hydroformylation reaction is selected from one of toluene, xylene, benzene, methyl tert-butyl ether, 1,4-dioxane, and tetrahydrofuran.
Citation Information
Patent Citations
Hetereocyclic agent as catalytic stabilizing agent in a hydroformylation process
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