Application of stabilizer in cobalt-catalyzed hydroformylation reaction

Abstract

The invention relates to an application of a stabilizer in cobalt-catalyzed hydroformylation reaction, which is characterized in that a compound containing an o-phenylenediamine structure is used as the stabilizer of a cobalt catalyst, and the stabilizer is matched with the cobalt catalyst for use to catalyze olefin and synthesis gas to generate hydroformylation reaction so as to realize recycling of the cobalt catalyst. The stability of a reaction system can be greatly improved, the cost of the catalyst can be reduced, meanwhile, the cobalt catalyst can be prevented from generating precipitates after the reaction, and the catalyst is always kept in a homogeneous phase in the reaction system, is convenient to directly distill and separate and can be directly recycled.

Description

Technical Field

[0001] The invention relates to the field of homogeneous catalysis, and in particular to application of a stabilizer in a cobalt-catalyzed hydroformylation reaction. Background Art

[0002] The cobalt-catalyzed hydroformylation reaction can efficiently convert olefins and synthesis gas. It is an important means of synthesizing aldehydes and alcohols, with an atom economy of up to 100%. Since the discovery of the hydroformylation reaction in 1938, the first generation of hydroformylation processes has used unmodified cobalt carbonyl as a catalyst under high temperature and high pressure. The recognized active species of unmodified cobalt carbonyl catalyst is HCo(CO)3, which is generated by the dissociation of a CO molecule from HCo(CO)4. There is a large amount of volatile HCo(CO)4 in the reaction system. This compound gradually decomposes when leaving the high-pressure CO atmosphere, forms a precipitate, and loses its catalytic activity. The subsequent process improved the separation and recovery method of cobalt. An alkaline aqueous solution was added to the hydroformylation reaction mixture to convert HCo(CO)4 into water-soluble [Co(CO)4] - After phase separation, the [Co(CO)4] - The aqueous phase is acidified by adding sulfuric acid in the presence of H2 / CO to regenerate [Co(H)(CO)4], which is then extracted from olefins and re-entered into the hydroformylation reaction (Exxon process). The above process avoids the deactivation of the cobalt catalyst and can be recycled after separation, but it requires the use of alkali and acid to extract the cobalt catalyst in a CO atmosphere.

[0003] The second generation process uses a Co catalyst system modified with a phosphine ligand. Although it reduces the catalyst activity, it improves the regional selectivity of the product. More importantly, the catalyst can be recycled. The phosphine ligand can protect the center of the cobalt catalyst. In the absence of a CO atmosphere, the cobalt catalyst always exists in a homogeneous form without precipitation. After the aldehyde and alcohol products are separated by distillation, the cobalt catalyst can re-enter the reactor to catalyze the olefin hydroformylation reaction. However, the price of phosphine ligands is relatively high, they are easily oxidized in the air, and they are highly toxic. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a stabilizer with low cost and good stability for use in cobalt-catalyzed hydroformylation reaction.

[0005] In order to solve the above problems, the present invention discloses an 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, and the stabilizer is used in combination with a cobalt catalyst to catalyze a hydroformylation reaction of olefins and synthesis gas, thereby realizing the recycling of the cobalt catalyst.

[0006] The stabilizer has a structure shown in general formula (I) or general formula (II): Where: R 1 , R 2 is an alkyl group, an aryl group or a hydrogen atom, and R 1 , R 2 Same or different; R 3 , R 4 is an alkyl group, an aryl group or a hydrogen atom, and R 3 , R 4 Same or different.

[0007] The molar concentrations of the stabilizer and the cobalt catalyst are both 1-10 mmol / L.

[0008] The cobalt catalyst is selected from one of octacarbonyl dicobalt, sodium cobalt carbonyl, cobalt acetate, cobalt acetylacetonate, cobalt isooctanoate, and cobalt cyclohexaneate.

[0009] The olefin is selected from one of pentene, hexene, octene, diisobutylene, dodecene, styrene and butadiene.

[0010] The synthesis gas is a mixture of carbon monoxide and hydrogen with a pressure of 4 to 10 MPa, wherein the volume ratio of carbon monoxide to hydrogen is 1:2 to 2:1.

[0011] The temperature of the hydroformylation reaction is 100 to 190 degrees Celsius, and the time is 1 to 24 hours.

[0012] The solvent for the hydroformylation reaction is selected from one of toluene, xylene, benzene, methyl tert-butyl ether, 1,4-dioxane and tetrahydrofuran.

[0013] Compared with the prior art, the present invention has the following advantages: 1. The present invention uses a compound containing an o-phenylenediamine structure as a stabilizer, which can avoid the formation of precipitation of the cobalt catalyst 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.

[0014] 2. The present invention uses a compound containing an o-phenylenediamine structure as a stabilizer, which can avoid the use of expensive and easily oxidized phosphine ligands. It has the advantages of low price, low toxicity and stability in the air, can greatly improve the stability of the reaction system, and can reduce the catalyst cost. DETAILED DESCRIPTION

[0015] Application of a stabilizer in cobalt-catalyzed hydroformylation reaction: a compound containing an o-phenylenediamine structure is used as a stabilizer for a cobalt catalyst, and the stabilizer is used in combination with a cobalt catalyst to catalyze the hydroformylation reaction of olefins and synthesis gas at a temperature of 100 to 190 degrees Celsius for 1 to 24 hours, thereby realizing the recycling of the cobalt catalyst.

[0016] Wherein: the stabilizer has a structure represented by general formula (I) or general formula (II): Where: R 1 , R 2 is an alkyl group, an aryl group or a hydrogen atom, and R 1 , R 2 Same or different; R 3 , R 4 is an alkyl group, an aryl group or a hydrogen atom, and R 3 , R 4 Same or different.

[0017] The molar concentrations of the stabilizer and the cobalt catalyst are both 1-10 mmol / L.

[0018] The cobalt catalyst is selected from one of octacarbonyl dicobalt, sodium cobalt carbonyl, cobalt acetate, cobalt acetylacetonate, cobalt isooctanoate and cobalt cyclohexaneate.

[0019] The olefin is selected from one of pentene, hexene, octene, diisobutylene, dodecene, styrene and butadiene.

[0020] Synthesis gas is a mixture of carbon monoxide and hydrogen with a pressure of 4~10 MPa, in which the volume ratio (L / L) of carbon monoxide to hydrogen is 1:2~2:1.

[0021] The solvent for the hydroformylation reaction is selected from one of toluene, xylene, benzene, methyl tert-butyl ether, 1,4-dioxane and tetrahydrofuran.

[0022] The specific process is as follows: According to the molar concentration (mmol / L), olefins and organic solvents are added to the reactor, stirred evenly to form a solution, and 1 to 10 parts of cobalt catalyst and 1 to 10 parts of compounds containing o-phenylenediamine structure are added to the above unit volume of solution, and the reactor is sealed. After the inert gas is exhausted from the air in the reactor, 4 to 10 MPa synthesis gas (the ratio of carbon monoxide to hydrogen is 1:2 to 2:1) is filled in, heated to 100 to 190 degrees Celsius, and reacted for 1 to 24 hours. After that, cool to room temperature, slowly exhaust the gas, open the reactor, take a liquid sample, dilute it, and detect it by gas chromatography.

[0023] When the catalyst is recycled, the mixture after the above reaction is distilled under reduced pressure, the distillation residue is added back into the reactor, a unit volume of olefin solution is added, and the reactor is sealed. After the inert gas is exhausted from the air in the reactor, the synthesis gas is refilled, heated to the reaction temperature, and samples are taken for analysis after the reaction is completed.

[0024] Example 1 Add 40 mL 1-octene and 160 mL toluene to a 500 mL reactor, stir evenly to form a solution, add 0.5 mmol octacarbonyl dicobalt and 1 mmol o-phenylenediamine to the above solution, and seal the reactor. After the inert gas is exhausted from the air in the reactor, fill it with 6 MPa of carbon monoxide and hydrogen in a ratio of 1:1, heat it to 140 degrees Celsius, react for 4 hours, cool it to room temperature, slowly exhaust the gas, open the reactor, take a liquid sample, dilute it, and detect it by gas chromatography. The olefin conversion rate is 96%, and the total yield of nonanal and nonanol is 87%. The mixture after the reaction is placed in the air without precipitation.

[0025] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 100 degrees Celsius, and the residue after distillation was mixed with 40 mL 1-octene and 160 mL toluene, added to the reactor, and the reactor was sealed. After the inert gas was exhausted from the air in the reactor, 6 MPa of carbon monoxide and hydrogen were filled with a 1:1 synthesis gas, heated to 140 degrees Celsius, reacted for 4 hours, and then cooled to room temperature. Sampling analysis showed that the olefin conversion rate was 95%, and the total yield of nonanal and nonanol was 88%.

[0026] Comparative Example Add 40 mL 1-octene and 160 mL toluene to a 500 mL reactor, stir evenly to form a solution, add 0.5 mmol octacarbonyl dicobalt to the above solution, and seal the reactor. After the inert gas is exhausted from the air in the reactor, fill it with 6 MPa of carbon monoxide and hydrogen in a ratio of 1:1, heat it to 140 degrees Celsius, react for 4 hours, cool it to room temperature, slowly exhaust the gas, open the reactor, take a liquid sample, dilute it, and detect it by gas chromatography. The olefin conversion rate is 96%, and the total yield of nonanal and nonanol is 87%. The mixture after the reaction is placed in the air, and a large amount of pink precipitate appears.

[0027] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 100 degrees Celsius, and the residue after distillation was mixed with 40 mL 1-octene and 160 mL toluene, added to the reactor, and the reactor was sealed. After the inert gas was exhausted from the air in the reactor, 6 MPa of carbon monoxide and hydrogen were filled with a 1:1 synthesis gas, heated to 140 degrees Celsius, reacted for 4 hours, and then cooled to room temperature. Sampling analysis showed that the olefin conversion rate was 45%, and the total yield of nonanal and nonanol was 19%.

[0028] Example 2 Add 40 mL of 1-pentene and 160 mL of benzene into a 500 mL reactor and stir to form a solution. Add 2 mmol of cobalt acetate and 2 mmol of N,N'-dimethyl-o-phenylenediamine (Formula I, R 1 = hydrogen atom, R 2= methyl), a closed reactor. After the inert gas was exhausted from the air in the reactor, a synthesis gas with a ratio of 4 MPa carbon monoxide and hydrogen of 1:1 was charged, heated to 100 degrees Celsius, reacted for 24 hours, cooled to room temperature, the gas was slowly exhausted, the reactor was opened, a liquid sample was taken, and after dilution, the gas chromatography test showed that the olefin conversion rate was 99%, and the total yield of hexanal and hexanol was 92%. The mixture after the reaction was placed in the air without precipitation.

[0029] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 60 degrees Celsius, and the residue after distillation was mixed with 40 mL of 1-pentene and 160 mL of benzene, added to the reactor, and the reactor was sealed. After the inert gas was exhausted from the air in the reactor, 4 MPa of synthesis gas with a carbon monoxide and hydrogen ratio of 1:1 was filled in, heated to 100 degrees Celsius, reacted for 24 hours, and then cooled to room temperature. Sampling analysis showed that the olefin conversion rate was 99%, and the total yield of hexanal and hexanol was 90%.

[0030] Example 3 40 mL of 1-hexene and 160 mL of methyl tert-butyl ether were added to a 500 mL reactor and stirred to form a solution. 0.2 mmol of cobalt acetylacetonate and 0.2 mmol of 2-phenylbenzimidazole (Formula II, R 3 = hydrogen atom, R 4 = phenyl), a closed reactor. After the inert gas was exhausted from the air in the reactor, 10 MPa of synthesis gas with a carbon monoxide and hydrogen ratio of 2:1 was filled in, heated to 150 degrees Celsius, reacted for 12 hours, cooled to room temperature, the gas was slowly exhausted, the reactor was opened, and a liquid sample was taken. After dilution, it was detected by gas chromatography, and the olefin conversion rate was 99%, and the total yield of heptanal and heptanol was 91%. The mixture after the reaction was placed in the air, and no precipitation occurred.

[0031] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 60 degrees Celsius, and the residue after distillation was mixed with 40 mL 1-hexene and 160 mL methyl tert-butyl ether, added to the reactor, and the reactor was sealed. After the inert gas was exhausted from the air in the reactor, 10MPa of carbon monoxide and hydrogen were filled with synthesis gas with a ratio of 2:1, heated to 150 degrees Celsius, reacted for 12 hours, and then cooled to room temperature. Sampling analysis showed that the olefin conversion rate was 99%, and the total yield of heptanal and heptanol was 93%.

[0032] Example 4 Add 40 mL of diisobutylene and 160 mL of 1,4-dioxane to a 500 mL reactor and stir to form a solution. Add 0.5 mmol of cobalt isooctanoate and 0.5 mmol of N-methyl-2-phenylbenzimidazole (Formula II, R 3 =Methyl, R4 = phenyl), a closed reactor. After the inert gas was exhausted from the air in the reactor, a synthesis gas with a ratio of 6 MPa carbon monoxide and hydrogen of 1:2 was charged, heated to 170 degrees Celsius, reacted for 1 hour, cooled to room temperature, the gas was slowly exhausted, the reactor was opened, a liquid sample was taken, and after dilution, the gas chromatography test showed that the olefin conversion rate was 88%, and the total yield of isononanal and isononanol was 67%. The mixture after the reaction was placed in the air without precipitation.

[0033] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 100 degrees Celsius, and the residue after distillation was mixed with 40 mL of diisobutylene and 160 mL of 1,4-dioxane, added to the reactor, and the reactor was sealed. After the inert gas was exhausted from the air in the reactor, 6 MPa of synthesis gas with a carbon monoxide and hydrogen ratio of 1:2 was filled in, heated to 170 degrees Celsius, reacted for 1 hour, and then cooled to room temperature. Sampling analysis showed that the olefin conversion rate was 90%, and the total yield of isononanal and isononanol was 65%.

[0034] Example 5 40 mL of dodecene and 160 mL of xylene were added to a 500 mL reactor and stirred to form a solution. 1 mmol of cobalt cyclohexaneate and 1 mmol of N-butyl-2-butylbenzimidazole (Formula II, R 3 =Butyl, R 4 = butyl), a closed reactor. After the inert gas was exhausted from the air in the reactor, a synthesis gas with a ratio of 6 MPa carbon monoxide and hydrogen of 1:1 was charged, heated to 190 degrees Celsius, reacted for 1 hour, cooled to room temperature, the gas was slowly exhausted, the reactor was opened, a liquid sample was taken, and after dilution, the gas chromatography test showed that the olefin conversion rate was 78%, and the total yield of tridecanal and tridecanol was 73%. The mixture after the reaction was placed in the air without precipitation.

[0035] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 120 degrees Celsius, and the residue after distillation was mixed with 40 mL of dodecene and 160 mL of xylene, added to the reactor, and the reactor was sealed. After the inert gas was exhausted from the air in the reactor, 6 MPa of carbon monoxide and hydrogen were filled with a 1:1 synthesis gas, heated to 190 degrees Celsius, reacted for 1 hour, and then cooled to room temperature. Sampling analysis showed that the olefin conversion rate was 79%, and the total yield of tridecanal and tridecanol was 68%.

[0036] Example 6 Add 20 mL of styrene and 180 mL of tetrahydrofuran into a 500 mL reactor and stir to form a solution. Add 1 mmol of sodium carbonylcobalt and 1 mmol of N,N'-diphenyl-o-phenylenediamine (Formula I, R 1= hydrogen atom, R 2 = phenyl), a closed reactor. After the inert gas was exhausted from the air in the reactor, a synthesis gas with a ratio of 6 MPa carbon monoxide and hydrogen of 1:1 was charged, heated to 100 degrees Celsius, reacted for 24 hours, cooled to room temperature, the gas was slowly exhausted, the reactor was opened, a liquid sample was taken, and after dilution, the gas chromatography test showed that the olefin conversion rate was 99%, and the total yield of phenylacetaldehyde and phenylethanol was 52%. The mixture after the reaction was placed in the air without precipitation.

[0037] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 100 degrees Celsius, and the residue after distillation was mixed with 20 mL of styrene and 180 mL of tetrahydrofuran, added to the reactor, and the reactor was sealed. After the inert gas was exhausted from the air in the reactor, 6 MPa of carbon monoxide and hydrogen were filled with a 1:1 synthesis gas, heated to 100 degrees Celsius, reacted for 24 hours, and then cooled to room temperature. Sampling analysis showed that the olefin conversion rate was 99%, and the total yield of phenylpropanaldehyde and phenylpropanol was 50%.

[0038] Example 7 200 mL of butadiene toluene solution was added to a 500 mL reactor. 1 mmol of sodium cobalt carbonyl and 1 mmol of N,N,N',N'-tetramethyl-o-phenylenediamine (Formula I, R 1 = R 2 = phenyl), a closed reactor. After the inert gas was exhausted from the air in the reactor, a synthesis gas with a ratio of 6 MPa carbon monoxide and hydrogen of 1:1 was charged, heated to 120 degrees Celsius, reacted for 4 hours, cooled to room temperature, the gas was slowly exhausted, the reactor was opened, a liquid sample was taken, and after dilution, the gas chromatography test showed that the olefin conversion rate was 99%, and the total yield of aldehydes and alcohols was 72%. The mixture after the reaction was placed in the air without precipitation.

[0039] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 80 degrees Celsius, and the residue after distillation was mixed with 20 mL of butadiene and 180 mL of tetrahydrofuran, added to the reactor, and the reactor was sealed. After the inert gas was exhausted from the air in the reactor, 6 MPa of carbon monoxide and hydrogen were filled with a 1:1 synthesis gas, heated to 120 degrees Celsius, reacted for 4 hours, and then cooled to room temperature. Sampling analysis showed that the olefin conversion rate was 99%, and the total yield of aldehydes and alcohols was 68%.

[0040] Example 8 40 mL of 2-octene and 160 mL of methyl tert-butyl ether were added to a 500 mL reactor and stirred to form a solution. 0.5 mmol of cobalt acetate and 0.5 mmol of 2-phenylbenzimidazole (Formula II, R 3 = hydrogen atom, R 4= phenyl), a closed reactor. After the inert gas was exhausted from the air in the reactor, a synthesis gas with a ratio of 6 MPa carbon monoxide and hydrogen of 1:1 was charged, heated to 150 degrees Celsius, reacted for 6 hours, cooled to room temperature, the gas was slowly exhausted, the reactor was opened, a liquid sample was taken, and after dilution, the gas chromatography test showed that the olefin conversion rate was 96%, and the total yield of heptanal and heptanol was 78%. The mixture after the reaction was placed in the air without precipitation.

[0041] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 90 degrees Celsius, and the residue after distillation was mixed with 40 mL of 2-octene and 160 mL of methyl tert-butyl ether, added to the reactor, and the reactor was sealed. After the inert gas was exhausted from the air in the reactor, 6 MPa of synthesis gas with a carbon monoxide and hydrogen ratio of 1:1 was filled in, heated to 150 degrees Celsius, reacted for 6 hours, and then cooled to room temperature. Sampling analysis showed that the olefin conversion rate was 97%, and the total yield of nonanal and nonanol was 76%.

[0042] Example 9 Add 40 mL of 2-hexene and 160 mL of tetrahydrofuran to a 500 mL reactor, stir evenly to form a solution, add 0.5 mmol of cobalt acetate and 0.5 mmol of o-phenylenediamine to the above solution, and seal the reactor. After the inert gas is exhausted from the air in the reactor, fill it with 6 MPa of synthesis gas with a carbon monoxide and hydrogen ratio of 1:1, heat it to 150 degrees Celsius, react for 6 hours, cool it to room temperature, slowly exhaust the gas, open the reactor, take a liquid sample, dilute it, and detect it by gas chromatography. The olefin conversion rate is 96%, and the total yield of heptanal and heptanol is 78%. And the mixture after the reaction is placed in the air, and no precipitation occurs.

[0043] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 60 degrees Celsius, and the residue after distillation was mixed with 40 mL 2-hexene and 160 mL tetrahydrofuran, added to the reactor, and the reactor was sealed. After the inert gas was exhausted from the air in the reactor, 6 MPa of carbon monoxide and hydrogen were filled with a 1:1 synthesis gas, heated to 150 degrees Celsius, reacted for 6 hours, and then cooled to room temperature. Sampling analysis showed that the olefin conversion rate was 97%, and the total yield of heptanal and heptanol was 76%.

[0044] Example 10 Add 40 mL of cyclopentene and 160 mL of tetrahydrofuran to a 500 mL reactor and stir to form a solution. Add 0.5 mmol of cobalt acetate, 0.5 mmol of 2-phenylbenzimidazole (general formula II, R 3 = hydrogen atom, R 4= phenyl), a closed reactor. After the inert gas was exhausted from the air in the reactor, a synthesis gas with a ratio of 6 MPa carbon monoxide and hydrogen of 1:1 was charged, heated to 120 degrees Celsius, reacted for 12 hours, cooled to room temperature, the gas was slowly exhausted, the reactor was opened, a liquid sample was taken, and after dilution, the gas chromatography test showed that the olefin conversion rate was 98%, and the total yield of hexanal and hexanol was 76%. The mixture after the reaction was placed in the air without precipitation.

[0045] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 60 degrees Celsius, and the residue after distillation was mixed with 40 mL of cyclopentene and 160 mL of tetrahydrofuran, added to the reactor, and the reactor was sealed. After the inert gas was exhausted from the air in the reactor, 6 MPa of carbon monoxide and hydrogen were filled with a 1:1 synthesis gas, heated to 120 degrees Celsius, reacted for 12 hours, and then cooled to room temperature. Sampling analysis showed that the olefin conversion rate was 98%, and the total yield of hexanal and hexanol was 76%.

[0046] Embodiment 11 Add 40 mL of cyclohexene and 160 mL of tetrahydrofuran to a 500 mL reactor, stir evenly to form a solution, add 0.5 mmol of cobalt acetate and 0.5 mmol of o-phenylenediamine to the above solution, and seal the reactor. After the inert gas is exhausted from the air in the reactor, fill it with 10 MPa of synthesis gas with a carbon monoxide and hydrogen ratio of 2:1, heat it to 100 degrees Celsius, react for 12 hours, cool it to room temperature, slowly exhaust the gas, open the reactor, take a liquid sample, dilute it, and detect it by gas chromatography. The olefin conversion rate is 98%, and the total yield of hexanal and hexanol is 89%. The mixture after the reaction is placed in the air, and no precipitation occurs.

[0047] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 70 degrees Celsius, and the residue after distillation was mixed with 40 mL of cyclohexene and 160 mL of tetrahydrofuran, added to the reactor, and the reactor was sealed. After the inert gas was exhausted from the air in the reactor, 10 MPa of synthesis gas with a carbon monoxide and hydrogen ratio of 2:1 was filled in, heated to 100 degrees Celsius, reacted for 12 hours, and then cooled to room temperature. Sampling analysis showed that the olefin conversion rate was 99%, and the total yield of hexanal and hexanol was 86%.

[0048] Example 12 40 mL of 1-hexene and 160 mL of methyl tert-butyl ether were added to a 500 mL reactor and stirred to form a solution. 0.5 mmol of cobalt acetate and 0.5 mmol of 2-phenylbenzimidazole (Formula II, R 3 = hydrogen atom, R 4= phenyl), a closed reactor. After the inert gas was exhausted from the air in the reactor, a synthesis gas with a ratio of 6 MPa carbon monoxide and hydrogen of 1:1 was charged, heated to 150 degrees Celsius, reacted for 6 hours, cooled to room temperature, the gas was slowly exhausted, the reactor was opened, a liquid sample was taken, and after dilution, the gas chromatography test showed that the olefin conversion rate was 99%, and the total yield of heptanal and heptanol was 88%. The mixture after the reaction was placed in the air without precipitation.

[0049] Catalyst recycling: The mixture after the above reaction was distilled under reduced pressure at 60 degrees Celsius, and the residue after distillation was mixed with 40 mL 1-hexene and 160 mL methyl tert-butyl ether, added to the reactor, and the reactor was sealed. After the inert gas was exhausted from the air in the reactor, 6 MPa of carbon monoxide and hydrogen were charged into the synthesis gas with a ratio of 1:1, heated to 150 degrees Celsius, reacted for 6 hours, and then cooled to room temperature. After opening the reactor, the above operation was repeated 5 times. The total conversion rate of olefins after 5 cycles was 95%, and the total yield of heptanal and heptanol was 85%.

Claims

1. Use 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. The stabilizer is used in combination with a cobalt catalyst to catalyze a hydroformylation reaction of olefins and synthesis gas, thereby realizing the recycling of the cobalt catalyst.

2. Use of a stabilizer according to claim 1 in a cobalt-catalyzed hydroformylation reaction, characterized in that: The stabilizer has a structure shown in general formula (I) or general formula (II): Where: R 1 , R 2 is an alkyl group, an aryl group or a hydrogen atom, and R 1 , R 2 Same or different; R 3 , R 4 is an alkyl group, an aryl group or a hydrogen atom, and R 3 , R 4 Same or different.

3. Use of a stabilizer according to claim 1 in a cobalt-catalyzed hydroformylation reaction, characterized in that: The molar concentrations of the stabilizer and the cobalt catalyst are both 1-10 mmol / L.

4. Use of a stabilizer according to claim 1 in a cobalt-catalyzed hydroformylation reaction, characterized in that: The cobalt catalyst is selected from one of octacarbonyl dicobalt, sodium cobalt carbonyl, cobalt acetate, cobalt acetylacetonate, cobalt isooctanoate, and cobalt cyclohexaneate.

5. Use of a stabilizer according to claim 1 in a cobalt-catalyzed hydroformylation reaction, characterized in that: The olefin is selected from one of pentene, hexene, octene, diisobutylene, dodecene, styrene and butadiene.

6. Use of a stabilizer according to claim 1 in a cobalt-catalyzed hydroformylation reaction, characterized in that: The synthesis gas is a mixture of carbon monoxide and hydrogen with a pressure of 4 to 10 MPa, wherein the volume ratio of carbon monoxide to hydrogen is 1:2 to 2:

1.

7. Use of a stabilizer according to claim 1 in a cobalt-catalyzed hydroformylation reaction, characterized in that: The temperature of the hydroformylation reaction is 100 to 190 degrees Celsius, and the time is 1 to 24 hours.

8. Use of a stabilizer according to claim 1 in a 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.

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