CN113122870B - Method for preparing vitamin A palmitate by electrochemical method - Google Patents
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Abstract
The invention aims to provide a method for preparing vitamin A palmitate by an electrochemical method, which takes a carbon nano rod loaded with metal oxide and metal sulfide as an anode and a Pt/C material as a cathode, and catalyzes vitamin A alcohol and palmitic acid to be electrolyzed in an electrolytic cell at a certain temperature to obtain vitamin A palmitate; the esterification reaction rate is improved, the obtained vitamin A palmitate is easy to crystallize, the esterification reaction has extremely high all-trans selectivity, the process is simple, the raw material cost is extremely low, and the method is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for preparing vitamin A palmitate by an electrochemical method.
Background
Vitamin A palmitate (vitamin A palmitate) is one of the main series of vitamin A products, vitamin A is an indispensable substance for normal metabolism of human bodies and animals, and has been widely applied to cosmetics, medicines, feeds and the like.
At present, the main synthetic routes of common vitamin A palmitate are chemical synthesis and biological enzyme methods. The chemical synthesis method mainly uses vitamin A alcohol and methyl palmitate as raw materials, and uses solid alkali such as potassium oxide and solid acid such as S2O8 2-/SnO2Protonic acid such as sulfuric acid, hydrochloric acid and the like are used as catalysts to carry out ester exchange catalytic reaction, the process is complex, the reaction condition is harsh, a large number of byproducts are generated, more acid-containing substances are generated, the separation is difficult, and the manufacturing cost is increased. The biological enzyme method mainly takes vitamin A acetate as a raw material, and generates vitamin A palmitate through esterification or ester exchange reaction in the presence of lipase, but the separation of the lipase after the reaction is difficult.
The electrochemical method is a method for controlling the transfer of electrons in an electrolytic cell under an external electric field so as to generate an electrocatalytic reaction on an electrode with catalytic activity, and is favored due to the advantages of high catalytic efficiency, few byproducts, environmental protection and the like. However, in the process of electrocatalytic esterification or ester exchange, because the electrolyte is in a weak acid environment, the electrode material has the defects of difficult hydrogen proton ionization, small specific surface area, poor conductivity, weak stability and the like, and the esterification or ester exchange reaction cannot be generally popularized in an electrocatalytic way, so that the preparation of the electrode material or the process suitable for the esterification or ester exchange reaction system has wide application prospect.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing vitamin A palmitate by an electrochemical method, wherein the single-walled carbon nanorods loaded with metal sulfides and oxides are prepared by an electrodeposition method and are used as electrode materials to catalyze and prepare the vitamin A palmitate, so that the esterification reaction rate is improved, the obtained vitamin A palmitate is easy to crystallize, the esterification reaction has extremely high all-trans selectivity, the process is simple, the raw material cost is extremely low, and the method is suitable for industrial production.
The invention provides a method for preparing vitamin A palmitate by an electrochemical method, which comprises the following steps: the method comprises the steps of taking a carbon nanorod loaded with metal oxide and metal sulfide as an anode, taking a Pt/C material as a cathode, adding a mixed solvent I, vitamin A alcohol and palmitic acid into an electrolytic cell, and electrolyzing at a certain temperature to obtain vitamin A palmitate.
In the carbon nano rod loaded with the metal oxide and the metal sulfide, the metal sulfide is one or more of sulfides of metal Fe, Co, Ti, Ni and preferably cobalt sulfide. The metal oxide is one or more of metal, Cr, V, Ce, Zn and Pb, and is preferably PbO2。
The metal oxide contains a large amount of oxygen vacancies, so that the activated carbonyl reactant can be adsorbed, and the catalytic efficiency is improved. A bridging bond can be formed between the metal oxide and the metal sulfide, and the metal oxide and the metal sulfide can be directly used as an electronic bridge to increase the conductivity of a system.
The preparation method of the anode electrode material comprises the following steps:
(1) adding the carbon fiber rod into a metal salt solution, introducing hydrogen sulfide gas under the stirring condition, filtering after reacting for a period of time, taking out the obtained solid carbon fiber rod, drying and then carrying out nitrogen sealing for later use.
(2) And (2) adding the electrodeposition solution into an electrolytic cell, placing the electrolytic cell at a certain temperature, taking the solid obtained in the step (1) as an electrode anode material, taking a non-metal graphite carbon rod as a cathode, and electrolyzing for a certain time at a certain constant current to prepare the composite electrode.
The metal salt in step (1) is a metal salt for preparing metal sulfide, is selected from one or more of salts of metal Fe, Co, Ti and Ni, can be nitrate, hydrochloride, sulfate, organic salt and the like, and is preferably a metal cobalt salt, such as cobalt nitrate, cobalt chloride, cobalt sulfate and cobalt phosphate, and is preferably cobalt nitrate.
The adding amount of the carbon fiber rods and the metal salt in the step (1) is as follows: the amount of the metal salt added in each gram of the carbon fiber rod is 0.01-1.0 mol, preferably 0.1-0.5 mol. The metal salt is dissolved by deionized water, and the molar concentration of the metal salt is 0.1-5 mol/L, preferably 0.5-2.5 mol/L. Preferably, the carbon fiber rod in step (1) of the present invention is a macroscopic cylindrical carbon rod formed by carbon nanotube enrichment, and has good chemical stability and electrical conductivity.
Preferably, in the step (1), the reaction time is 0.5-10 hours, preferably 1-5 hours.
In the step (2) of the invention, the electrodeposition solution is a mixture of a precursor salt of a metal oxide and a fluorine-containing compound, and the precursor salt of the metal oxide is a salt containing one or more of metal Cr, V, Ce, Zn and Pb, preferably a metal lead salt. The metal lead salt is one or more of lead nitrate, lead sulfate, lead chloride, lead acetylacetonate and the like, and lead nitrate is preferred. The addition of the fluorine-containing compound selected from one or more of sodium fluoride, potassium fluoride, hydrofluoric acid, lithium fluoride and the like, preferably sodium fluoride, can greatly increase the electron conductivity of electrodeposition, thereby more uniformly depositing metal oxide on carbon fibers. The molar ratio of the precursor salt of the metal oxide to the fluorine-containing compound is 0.1: 1-10: 1, preferably 0.5: 1-5: 1. The molar concentration of the precursor salt of the metal oxide is 0.1-5 mol/L, preferably 0.5-2.5 mol/L. The amount of the precursor salt of the metal oxide added to each gram of the carbon fiber rod is 0.001-0.2 mol, preferably 0.01-0.05 mol.
In the step (2), the temperature of the electrolytic cell is 10-50 ℃, preferably 20-40 ℃, and the current density is 1-50 mA/cm2Preferably 5 to 30mA/cm2The deposition time is 1-10 h, preferably 2-6 h.
In the present invention, the mixed solvent one is a mixture of an organic alcohol and an aqueous solution of an inorganic salt, the organic alcohol is one or more selected from methanol, ethanol, n-butanol, ethylene glycol, propylene glycol, isopropanol, etc., preferably methanol, and the inorganic salt is one or more selected from sodium chloride, sodium sulfate, sodium carbonate, sodium bicarbonate, potassium chloride, etc., preferably sodium chloride. The molar concentration of the inorganic salt in the aqueous solution of the inorganic salt in the first mixed solvent is 0.1-5 mol/L, preferably 0.5-2.5 mol/L. The volume ratio of the aqueous solution of the inorganic salt to the organic alcohol is 0.1: 1-5: 1, preferably 0.5: 1-2: 1.
In the invention, the molar ratio of the vitamin A alcohol to the palmitic acid is 1: 1-1: 1.5, preferably 1: 1.05-1: 1.35. The volume of the organic alcohol added to each mole of the vitamin A alcohol is 100-1000 mL, preferably 200-600 mL.
In the method for preparing the vitamin A palmitate, the anode material used for electrolysis is the prepared sulfide and oxide loaded single-walled carbon nanorod, the cathode material is a noble metal electrode Pt/C, the temperature of the electrolysis reaction is 10-100 ℃, preferably 30-70 ℃, the electrolysis reaction is carried out under constant current, and the current density is 5-100 mA/cm2Preferably 10 to 50mA/cm2The reaction time is 1-10 h, preferably 3-7 h, and the reaction pressure is normal pressure-0.5 MPa, preferably normal pressure.
In the method for preparing the vitamin A palmitate, the product obtained by the extraction reaction is added with the organic solvent after the electrolysis reaction is finished, and the content of the product is analyzed by a liquid phase.
The first organic solvent is one or more of petroleum ether, n-hexane, n-heptane, tetrahydrofuran and dichloromethane, preferably petroleum ether. The addition amount of the organic solvent I is as follows: the volume of the organic solvent I added into each mole of the vitamin A alcohol is 100-1000 mL, preferably 300-700 mL.
Collecting the obtained extract phase, concentrating under negative pressure, adding a certain amount of crystallization reagent, crystallizing at low temperature, and analyzing the obtained product crystal in liquid phase to obtain vitamin A palmitate with high purity.
Preferably, the crystallization agent is one or more of toluene, ethyl acetate, acetonitrile, ethanol, isopropanol, and the like, preferably toluene. Calculating the amount of the crystallization reagent added in the reaction according to the theoretically obtained amount of the vitamin A palmitate, wherein the volume of the crystallization reagent added for theoretically generating 1 g of the vitamin A palmitate is 1-20 mL, preferably 5-20 mL. The crystallization temperature is-10 to 30 ℃, and preferably 0 to 15 ℃.
The invention has the beneficial effects that:
(1) the composite electrode material has good chemical stability and can be suitable for an acid-containing system in the esterification reaction of the vitamin A palmitate for a long time. In addition, the obtained composite electrode has a large specific surface area, the esterification reaction of the vitamin A palmitate is coupled with electrochemical catalysis by using the electrode material, the unit esterification reaction rate is improved, and the composite electrode is green and environment-friendly;
(2) inorganic acid and alkali or a biological enzyme catalyst is not required to be added in the production process, the process is simple, and the cost of raw materials is extremely low;
(3) the generated product is easy to crystallize, the esterification reaction has extremely high all-trans selectivity, and the product has more physiological activity when being used for human nutrition and provides feasible support for industrial production.
Detailed Description
The reagents used in the invention, namely the carbon nano rod, the graphite carbon rod, the cobalt nitrate, the nickel nitrate, the lead nitrate, the sodium fluoride, the noble metal Pt/C electrode and the petroleum ether, are purchased from Shanghai Tantanktechnology, Inc., and the vitamin A alcohol (namely the retinol) is purchased from Basff chemical industry, Inc.
Example 1
(1) And (2) placing 20g of carbon fiber rod in 2L of 0.5mol/L cobalt nitrate aqueous solution, introducing sufficient hydrogen sulfide gas into the solution under strong stirring, controlling the gas introduction time, reacting metal salt and gas for 1h, taking out the obtained carbon fiber rod adsorbing precipitates, drying, and carrying out nitrogen sealing for later use.
(2) Preparing 500mL of 0.5mol/L lead nitrate aqueous solution, adding 0.5mol of sodium fluoride, stirring uniformly, dissolving completely, adding into an electrolytic cell, and at 20 deg.C, taking the dried solid as an electrode anode, a graphite carbon rod sheet as a cathode, and at 5mA/cm2Bottom, electrodeposition2h, preparing PbO2@C@Co2S3An electrode having a specific surface area of 200.5m as analyzed by BET characterization2(ii) in terms of/g. The prepared electrode is placed in a methanol solution of palmitic acid and stands for 24 hours, the mass change before and after weighing is carried out, the measured mass loss rate is only 0.02 percent, and the obtained composite electrode material has good chemical stability and can be suitable for an acid-containing system in the esterification reaction of vitamin A palmitate for a long time.
(3) 200mL of methanol and 100mL of 0.5mol/L sodium chloride solution are added into an electrolytic cell, and 286.5g of vitamin A alcohol and 268.8g of palmitic acid are added into the electrolytic cell after the solution is stirred uniformly. PbO prepared by the step (2)2@C@Co2S3The electrode is an electrolytic anode, Pt/C is an electrolytic cathode, and the current density is 10mA/cm2The reaction temperature is 30 ℃, and the electrolysis is carried out for 3 hours at the anode under the normal pressure. After the reaction, the concentration of vitamin A alcohol in the mixed solution was sampled and analyzed, and the reaction conversion rate was calculated to be 98.5%, and the average reaction rate was calculated to be 4.56X 10-6And adding 300mL of petroleum ether into the mixture to extract a product, wherein the yield of the vitamin A palmitate is 90.3% and the all-trans selectivity is 94.4% according to analysis. Concentrating and desolventizing the extract phase containing the product under negative pressure, adding the extract phase into 2500mL of toluene, and performing low-temperature cooling crystallization at 0 ℃, wherein the purity of the obtained crystal is 98.6% by liquid chromatography analysis.
Example 2
(1) And (2) placing 20g of carbon fiber rod in 4.0L of 2.5mol/L of cobalt nitrate aqueous solution, introducing sufficient hydrogen sulfide gas into the solution under strong stirring, controlling the gas introduction time, reacting metal salt and gas for 5 hours, taking out the obtained carbon fiber rod adsorbing precipitates, drying, and carrying out nitrogen sealing for later use.
(2) Preparing 400mL of 2.5mol/L lead nitrate aqueous solution, adding 0.2mol of sodium fluoride into the aqueous solution, stirring the solution uniformly, dissolving the solution completely, and adding the solution into an electrolytic cell. At 40 deg.C, the dried solid is used as electrode anode, graphite carbon rod sheet is used as cathode, and the concentration of carbon rod sheet is 30mA/cm2Then, electrodepositing for 6h to prepare PbO2@C@Co2S3An electrode having a specific surface area of 240.7m as analyzed by BET characterization2(ii) in terms of/g. Will prepareThe obtained electrode is placed in a methanol solution of palmitic acid and stands for 24 hours, the mass change before and after weighing is carried out, the measured mass loss rate is only 0.05 percent, and the obtained composite electrode material has good chemical stability and can be suitable for an acid-containing system in the esterification reaction of vitamin A palmitate for a long time.
(3) 600mL of methanol and 1200mL of 2.5mol/L sodium chloride solution are added into an electrolytic cell, and 286.5g of vitamin A alcohol and 384.0g of palmitic acid are added into the electrolytic cell after the solution is stirred uniformly. PbO prepared by the step (2)2@C@Co2S3Is used as an electrolytic anode, Pt/C is used as an electrolytic cathode, and the current density is 50mA/cm2The electrolysis was carried out at a reaction temperature of 70 ℃ and 0.5MPa for 7h at the anode. After the reaction, the concentration of vitamin A alcohol in the mixed solution is sampled and analyzed, the reaction conversion rate is calculated to be 99.2 percent, and the average reaction rate is 5.96 multiplied by 10-6And adding 700mL of petroleum ether into the mixture to extract a product, wherein the yield of the vitamin A palmitate is 92.3% and the all-trans selectivity is 96.4% according to analysis. Concentrating the extract phase containing the product under negative pressure to remove solvent, adding into 5L of toluene, and crystallizing at 15 deg.C under low temperature to obtain crystal with purity of 99.1% by liquid chromatography.
Example 3
(1) And (2) placing 20g of carbon fiber rod in 2L of 0.5mol/L nickel nitrate aqueous solution, introducing sufficient hydrogen sulfide gas into the solution under strong stirring, controlling the gas introduction time, reacting metal salt and gas for 1h, taking out the obtained carbon fiber rod adsorbing the precipitate, drying, and carrying out nitrogen sealing for later use.
(2) 500mL of 0.5mol/L lead nitrate aqueous solution is prepared, 0.5mol of sodium fluoride is added into the aqueous solution, the solution is dissolved completely after being stirred uniformly, and the solution is added into an electrolytic cell. At 20 deg.C, the dried solid is used as electrode anode, graphite carbon rod sheet is used as cathode, and the concentration of carbon rod sheet is 5mA/cm2Then, electrodepositing for 2h to prepare PbO2@ C @ NiS electrode, with a specific surface area of 189.5m as analyzed by BET characterization2(ii) in terms of/g. Placing the prepared electrode in a methanol solution of palmitic acid for standing for 24h, weighing the mass change before and after the electrode is placed in the methanol solution of the palmitic acid, and determining that the mass loss rate is only 0.07 percent, which shows that the obtained composite electrode material has good chemical stabilityQualitative and long-term application to the acid-containing system in the esterification reaction of the vitamin A palmitate.
(3) 200mL of methanol and 100mL of 0.5mol/L sodium chloride solution are added into an electrolytic cell, and 286.5g of vitamin A alcohol and 268.8g of palmitic acid are added into the electrolytic cell after the solution is stirred uniformly. With PbO2@ C @ NiS as electrolytic anode and Pt/C as electrolytic cathode at current density of 10mA/cm2The reaction temperature is 30 ℃, and the electrolysis is carried out for 3 hours at the anode under the normal pressure. After the reaction, a sample was taken and analyzed to obtain a mixture of 3.74X 10-6And adding 300mL of petroleum ether into the mixture to extract a product, wherein the yield of the vitamin A palmitate is 85.3% and the all-trans selectivity is 89.3%. Concentrating the extract phase containing the product under negative pressure to remove solvent, adding into 10L of toluene, and crystallizing at 5 deg.C under low temperature to obtain crystal with purity of 92.5% by liquid chromatography.
Example 4
(1) And (2) placing 20g of carbon fiber rod in 2L of 0.5mol/L cobalt nitrate aqueous solution, introducing sufficient hydrogen sulfide gas into the solution under strong stirring, controlling the gas introduction time, reacting metal salt and gas for 1h, taking out the obtained carbon fiber rod adsorbing precipitates, drying, and carrying out nitrogen sealing for later use.
(2) 500mL of 0.5mol/L zinc nitrate aqueous solution is prepared, 0.5mol of sodium fluoride is added into the aqueous solution, the solution is dissolved completely after being stirred uniformly, and the solution is added into an electrolytic cell. At 20 deg.C, the dried solid is used as electrode anode, graphite carbon rod sheet is used as cathode, and the concentration of carbon rod sheet is 5mA/cm2Then, electrodepositing for 2h to prepare ZnO @ C @ Co2S3An electrode having a specific surface area of 178.2m as analyzed by BET characterization2(ii) in terms of/g. The prepared electrode is placed in a methanol solution of palmitic acid and stands for 24 hours, the mass change before and after weighing is carried out, the measured mass loss rate is only 0.11 percent, and the obtained composite electrode material has good chemical stability and can be suitable for an acid-containing system in the esterification reaction of vitamin A palmitate for a long time.
(3) 200mL of methanol and 100mL of 0.5mol/L sodium chloride solution are added into an electrolytic cell, and 286.5g of vitamin A alcohol and 268.8g of palmitic acid are added into the electrolytic cell after the solution is stirred uniformly. With ZnO @ C @ Co2S3Is used as an electrolytic anode, Pt/C is used as an electrolytic cathode, and the current density is 10mA/cm2The reaction temperature is 30 ℃, and the electrolysis is carried out for 3 hours at the anode under the normal pressure. After the reaction, the concentration of vitamin A alcohol in the mixed solution was sampled and analyzed, and the reaction conversion rate was calculated to be 88.5%, and the average reaction rate was calculated to be 2.12X 10-6And adding 300mL of petroleum ether into the mixture to extract a product, wherein the yield of the vitamin A palmitate is 85.3% and the all-trans selectivity is 87.2% according to analysis. Concentrating and desolventizing the extract phase containing the product under negative pressure, adding the extract phase into 3L of toluene, and performing low-temperature cooling crystallization at 0 ℃ to obtain crystals with the purity of 81.3% by liquid chromatography analysis.
Example 5
(1) And (2) placing 20g of carbon fiber rod in 2L of 0.5mol/L ferric nitrate aqueous solution, introducing sufficient hydrogen sulfide gas into the solution under strong stirring, controlling the gas introduction time, reacting metal salt and gas for 1h, taking out the obtained carbon fiber rod adsorbing the precipitate, drying, and sealing with nitrogen for later use.
(2) 500mL of 0.5mol/L chromium nitrate aqueous solution is prepared, 0.5mol of sodium fluoride is added into the aqueous solution, and the solution is completely dissolved after being uniformly stirred. At 20 deg.C, the dried solid is used as electrode anode, graphite carbon rod sheet is used as cathode, and the concentration of carbon rod sheet is 5mA/cm2Then, electrodepositing for 2h to prepare Cr2O3@C@Fe2S3An electrode having a specific surface area of 140.8m as analyzed by BET characterization2(ii) in terms of/g. The prepared electrode is placed in a methanol solution of palmitic acid and stands for 24 hours, the mass change before and after weighing is carried out, the measured mass loss rate is only 0.22 percent, and the obtained composite electrode material has good chemical stability and can be suitable for an acid-containing system in the esterification reaction of vitamin A palmitate for a long time.
(3) 200mL of methanol and 100mL of 0.5mol/L sodium chloride solution are added into an electrolytic cell, and 286.5g of vitamin A alcohol and 268.8g of palmitic acid are added into the electrolytic cell after the solution is stirred uniformly. With PbO2@C@Co2S3Is used as an electrolytic anode, Pt/C is used as an electrolytic cathode, and the current density is 10mA/cm2The reaction temperature is 30 ℃, and the electrolysis is carried out for 3 hours at the anode under the normal pressure. Sampling, analyzing and mixing after the reaction is finishedThe concentration of vitamin A alcohol in the solution was calculated to be 98.5% conversion and the average reaction rate was 1.16X 10-6And adding 300mL of petroleum ether into the mixture to extract a product, wherein the yield of the vitamin A palmitate is 87.3% and the all-trans selectivity is 60.4% according to analysis. Concentrating the extract phase containing the product under negative pressure to remove solvent, adding into 5L of toluene, and crystallizing at 0 deg.C under low temperature to obtain crystal with purity of 74.7% by liquid chromatography.
Comparative example 1
100mL of methanol and 200mL of 0.5mol/L sodium chloride solution are added into an electrolytic cell, and 286.5g of vitamin A alcohol and 268.8g of palmitic acid are added into the electrolytic cell after the mixture is uniformly stirred. Taking a graphite carbon rod as an electrolysis anode and Pt/C as an electrolysis cathode, and controlling the current density to be 10mA/cm2The reaction temperature is 30 ℃, and the electrolysis is carried out for 3 hours at the anode under the normal pressure. After the reaction, the concentration of vitamin A alcohol in the mixed solution is sampled and analyzed, the reaction conversion rate is calculated to be 40.2 percent, and the average reaction rate is 1.86 multiplied by 10-6mol/g.s, and then 300mL of dichloromethane is added to extract the product, the yield of the vitamin A palmitate is 36.53 percent and the all-trans selectivity is 54.7 percent. Concentrating the extract phase containing the product under negative pressure to remove solvent, adding into 5L of toluene, and crystallizing at 0 deg.C under low temperature to obtain crystal with purity of 70.9% by liquid chromatography.
According to the comparative example, the yield of the vitamin A palmitate synthesized by the electrocatalytic reaction is low on the premise of no loading of the metal oxide and the metal sulfide.
Claims (41)
1. The method for preparing the vitamin A palmitate by the electrochemical method is characterized by comprising the following steps: adding a mixed solvent I, vitamin A alcohol and palmitic acid into an electrolytic cell by taking a carbon nanorod loaded with metal oxide and metal sulfide as an anode and a Pt/C material as a cathode, and electrolyzing at a certain temperature to obtain vitamin A palmitate;
in the carbon nano rod loaded with the metal oxide and the metal sulfide, the metal sulfide is one or more of sulfides of metal Fe, Co, Ti and Ni, and the metal oxide is one or more of oxides of metal Cr, V, Ce, Zn and Pb;
the first mixed solvent is a mixture of organic alcohol and an aqueous solution of inorganic salt.
2. The method of claim 1, wherein the metal sulfide is a cobalt sulfide; the metal oxide is PbO2。
3. The method according to claim 1, wherein the anode electrode material is prepared by the following steps:
(1) adding carbon nanorods into a metal salt solution, introducing hydrogen sulfide gas under the condition of stirring, filtering after reacting for a period of time, taking out the obtained solid carbon nanorods, drying and carrying out nitrogen sealing for later use;
(2) and (2) adding the electrodeposition solution into an electrolytic cell, placing the electrolytic cell at a certain temperature, taking the solid obtained in the step (1) as an electrode anode material, taking a non-metal graphite carbon rod as a cathode, and electrolyzing for a certain time under constant current to prepare the composite electrode.
4. The method according to claim 3, wherein the metal salt in step (1) is a metal salt for preparing metal sulfide, and is selected from one or more of salts of metals Fe, Co, Ti and Ni.
5. The method according to claim 4, wherein the metal salt in the step (1) is a metal salt for preparing metal sulfide, and is a metal Co salt.
6. The method of claim 3, wherein the addition amount of the carbon nanorods and the metal salt in the step (1) is as follows: the amount of the metal salt added in each gram of carbon nano rod is 0.01-1.0 mol.
7. The method of claim 6, wherein the addition amount of the carbon nanorods and the metal salt in the step (1) is as follows: the amount of the metal salt added in each gram of carbon nano rod is 0.1-0.5 mol.
8. The method according to claim 3, wherein the reaction time in step (1) is 0.5-10 h.
9. The method according to claim 8, wherein in the step (1), the reaction time is 1-5 h.
10. The method of claim 3 wherein the bath in step (2) is a mixture of a metal oxide precursor salt and a fluorine-containing compound, the metal oxide precursor salt being one or more of the metal-containing salts of Cr, V, Ce, Zn, Pb.
11. The method of claim 10 wherein the bath in step (2) is a mixture of a metal oxide precursor salt and a fluorine-containing compound, the metal oxide precursor salt being a metal lead-containing salt.
12. The method of claim 11, wherein the metallic lead salt is one or more of lead nitrate, lead sulfate, lead chloride, and lead acetylacetonate.
13. The method of claim 12, wherein the metallic lead salt is lead nitrate.
14. The method according to claim 10, wherein the fluorine-containing compound is selected from one or more of sodium fluoride, potassium fluoride, hydrofluoric acid, and lithium fluoride.
15. The method of claim 14, wherein the fluorine-containing compound is sodium fluoride.
16. The method according to claim 10, wherein the precursor salt of the metal oxide and the fluorine-containing compound are added in a molar ratio of 0.1:1 to 10: 1.
17. The method of claim 16, wherein the precursor salt of the metal oxide and the fluorine-containing compound are added in a molar ratio of 0.5:1 to 5: 1.
18. The method of claim 10, wherein the amount of the precursor salt of the metal oxide added per gram of the carbon nanorods is 0.001-0.2 mol.
19. The method of claim 18, wherein the amount of the precursor salt of the metal oxide added per gram of the carbon nanorods is 0.01-0.05 mol.
20. The method as claimed in claim 3, wherein the temperature of the electrolytic cell in the step (2) is 10 to 50 ℃ and the current density is 1 to 50mA/cm2The deposition time is 1-10 h.
21. The method as claimed in claim 20, wherein the temperature of the electrolytic cell in the step (2) is 20 to 40 ℃ and the current density is 5 to 30mA/cm2The deposition time is 2-6 h.
22. The method according to claim 1, wherein the organic alcohol is one or more of methanol, ethanol, n-butanol, ethylene glycol, propylene glycol, isopropanol; the inorganic salt is one or more of sodium chloride, sodium sulfate, sodium carbonate, sodium bicarbonate and potassium chloride.
23. The method of claim 22, wherein the organic alcohol is methanol; the inorganic salt is sodium chloride.
24. The method of claim 1, wherein the volume of organic alcohol added per mole of retinol is 100-1000 mL.
25. The method of claim 24, wherein the volume of organic alcohol added per mole of retinol is 200-600 mL.
26. The method according to claim 1, wherein the molar ratio of retinol to palmitic acid is 1:1 to 1: 1.5.
27. The method of claim 26, wherein the molar ratio of retinol to palmitic acid is from 1:1.05 to 1: 1.35.
28. The method according to claim 1, wherein the temperature of the electrolysis reaction is 10 to 100 ℃.
29. The method of claim 28, wherein the temperature of the electrolysis reaction is 30 to 70 ℃.
30. The method according to claim 1, wherein the electrolysis is carried out under a constant current at a current density of 5 to 100mA/cm2The reaction time is 1-10 h, and the reaction pressure is normal pressure-0.5 MPa.
31. The method of claim 30, wherein the electrolysis is carried out under a constant current with a current density of 10 to 50mA/cm2The reaction time is 3-7 h, and the reaction pressure is normal pressure.
32. The method of claim 1, wherein the electrolysis is terminated and an organic solvent is added to extract the product obtained from the reaction.
33. The method of claim 32, wherein the organic solvent is one or more of petroleum ether, n-hexane, n-heptane, tetrahydrofuran, and dichloromethane.
34. The method of claim 33, wherein the first organic solvent is petroleum ether.
35. The method of claim 32, wherein the first organic solvent is added in an amount of: the volume of the organic solvent I added into each mole of vitamin A alcohol is 100-1000 mL.
36. The method of claim 35, wherein the first organic solvent is added in an amount of: the volume of the organic solvent I added into each mole of vitamin A alcohol is 300-700 mL.
37. The process according to claim 1, characterized in that the product obtained after the reaction is crystallized out using a crystallization reagent.
38. The method of claim 37, wherein the crystallization reagent is one or more of toluene, ethyl acetate, acetonitrile, ethanol, isopropanol.
39. The method of claim 38, wherein the crystallization agent is toluene.
40. The method of claim 37, wherein the crystallization temperature is-10 to 30 ℃.
41. The method of claim 40, wherein the crystallization temperature is 0-15 ℃.
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