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CN114534729B - Catalyst, preparation method thereof and application of catalyst in preparation of beta-carotene by electrochemical method - Google Patents

Catalyst, preparation method thereof and application of catalyst in preparation of beta-carotene by electrochemical method Download PDF

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CN114534729B
CN114534729B CN202210213963.4A CN202210213963A CN114534729B CN 114534729 B CN114534729 B CN 114534729B CN 202210213963 A CN202210213963 A CN 202210213963A CN 114534729 B CN114534729 B CN 114534729B
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catalyst
mass
oxide
reaction
ferrite
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CN114534729A (en
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张弈宇
王婕
接鲸瑞
沈宏强
宋军伟
张涛
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Wanhua Chemical Group Co Ltd
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Abstract

The invention discloses a catalyst, a preparation method thereof and application thereof in preparing beta-carotene by an electrochemical method. The catalyst is specifically a graphene-supported metal ferrite and metal oxide catalyst. The method comprises the steps of taking an aqueous solution of vitamin A triphenylphosphine salt as an electrolyte, and carrying out electrolytic reaction in the presence of the catalyst and alkali to prepare the beta-carotene. The method has high product yield, avoids the use of an oxidant in the traditional process, and is high in safety and environment-friendly. The method also has the advantages of high yield (up to more than 90%) of the beta-carotene, recycling of the catalyst and electrolyte, small waste water amount and the like.

Description

Catalyst, preparation method thereof and application of catalyst in preparation of beta-carotene by electrochemical method
Technical Field
The invention belongs to the technical field of beta-carotene preparation, and relates to a catalyst, a preparation method of the catalyst and application of the catalyst in preparing beta-carotene by an electrochemical method.
Background
Beta-carotene (beta-Carotene, molecular formula C 40H56, structure shown in the following formula) is an antioxidant, has detoxification function, is an essential nutrient for maintaining human health, is widely applied to industries such as medicines, foods, cosmetics, feed additives, dyes and the like, and has good market prospect.
The prior art discloses processes for preparing beta-carotene from vitamin A and its derivatives as starting materials, which include Bernhard Schulz et al (Bernhard Schulz, etal, U.S. Pat. No. 4,105,855, manufacture ofn Symmetrical Carotenoids, [ P ] 1978), and provides a method for isomerising beta-carotene after the steps of reacting a C20 phosphine salt with a peroxide in the presence of a base to form a solid, and extracting, washing, removing the solvent, and the like.
The method has low yield, and the peroxide used in the reaction process can oxidize beta-carotene, so that the safety risk is high.
CN101081829a discloses a process for the preparation of beta-carotene by oxidation of C20 phosphine salts in two phases of water and non-water soluble solvents, by extraction of the beta-carotene formed into the organic phase, thereby avoiding oxidation by aqueous phase oxidants. The method has low yield, and the beta-carotene has relatively small solubility in the organic solvent, so that a large amount of solvent is needed to be dissolved, and a large amount of wastewater is generated by the method to be treated, which is unfavorable for industrial amplification, and the existence of the oxidant also has safety risk.
In the method disclosed in CN101041631A, sodium hypochlorite is adopted as an oxidant, so that the safety of the oxidant is improved, but the reaction is also carried out under a two-phase condition, and the yield is low and is only about 40%.
CN110452147a discloses a method of adding palladium catalyst and cyclodextrin substance as phase transfer catalyst by using molecular oxygen as oxidant. The method has higher yield, but needs to be carried out under higher pressure, and has certain safety risk, and the use of water and organic solvents also brings the problem that a large amount of wastewater needs to be treated.
CN107653459a discloses a process for preparing beta-carotene by electrochemically oxidizing C20 phosphine salt. The method uses electrolyzed water to generate oxygen for oxidation, avoids the use of traditional oxidants, reduces reaction risks, and has a more environment-friendly route. However, the method has the problems of high alkali consumption, low reaction yield and insufficient oxygen utilization.
In summary, in the process for preparing beta-carotene by oxidative coupling of C20 phosphine salt disclosed in the prior art, the problems of low reaction yield, certain safety risk in the use of an oxidant and large amount of wastewater generated after the reaction still exist. There is thus a need to develop a new process for the preparation of beta-carotene which solves the above problems.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a catalyst and a method for preparing the same, which can be used in a method for preparing beta-carotene from vitamin a triphenylphosphine salt (C20 phosphine salt) by electrochemical means. The electrochemical method provided by the invention not only avoids the use of an oxidant in the traditional process, but also has the advantages of high safety, environmental protection, high product yield, recycling and reuse of the catalyst and the like.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The invention provides a catalyst which can be used for preparing beta-carotene electrochemically, in particular to a graphene-supported metal ferrite and metal oxide catalyst, wherein, based on the mass of a graphene carrier,
The loading of the metallic ferrite is 4-10wt%, for example 4.5wt%, 5.5wt%, 6.5wt%, 7.5wt%, 8.5wt%, 9.5wt%, preferably 5-7wt%;
The metal oxide is supported in an amount of 10 to 25wt%, for example 12wt%, 14wt%, 16wt%, 18wt%, 20wt%, 22wt%, preferably 15 to 20wt%.
In the present invention, the metallic ferrite is selected from ferrite of a fourth-period transition metal, including any one or a combination of at least two of manganese ferrite (MnFe 2O4), cobalt ferrite (CoFe 2O4), zinc ferrite (ZnFe 2O4), nickel ferrite (NiFe 2O4), copper ferrite (CuFe 2O4), preferably nickel ferrite (NiFe 2O4).
In the present invention, the metal oxide is selected from a fourth and a fifth period transition metal oxide, and any one or a combination of at least two of titanium oxide (TiO 2), chromium oxide (Cr 2O3), cobalt oxide (CoO), manganese dioxide (MnO 2), nickel oxide (NiO), copper oxide (CuO), zinc oxide (ZnO), yttrium oxide (Y 2O3) and zirconium oxide (ZrO 2), preferably cobalt oxide (CoO).
The invention also provides a preparation method of the catalyst, which comprises the following steps:
mixing graphene oxide with water to obtain graphene oxide dispersion liquid, then ultrasonically mixing the graphene oxide dispersion liquid with metal ferrite, adding a metal oxide precursor and a reducing agent into the mixture, fully stirring the mixture, performing hydrothermal reaction at 150-220 ℃ such as 160 ℃, 170 ℃, 180 ℃, 190 ℃,200 ℃, 210 ℃, preferably 180-200 ℃ for 10-18 hours such as 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours and 17 hours, preferably 12-15 hours, and washing and drying the mixture after the reaction is completed to obtain the catalyst.
In the preparation method of the invention, the graphene oxide dispersion liquid has the mass of water which is 100-300 times, such as 125 times, 150 times, 175 times, 200 times, 225 times, 250 times, 275 times, preferably 200-250 times, of the mass of the graphene oxide.
In the preparation method of the invention, the mass of the metal ferrite is 4-10% of that of the graphene oxide, such as 4.5%, 5.5%, 6.5%, 7.5%, 8.5%, 9.5%, and preferably 5-7%; the metallic ferrite corresponds to the metallic ferrite in the catalyst, namely, the ferrite selected from the fourth-period transition metals.
In the preparation method of the invention, the mass of the metal oxide precursor is 10-30% of that of graphene oxide, for example 12.5%, 15.0%, 17.5%, 20.0%, 22.5%, 25.0%, 27.5%, preferably 15-20%;
Preferably, the metal oxide precursor is selected from metal soluble salts, and metal elements in the metal soluble salts correspond to metal elements contained in the metal oxide in the catalyst, namely are selected from fourth and fifth period transition metals;
The metal soluble salt is more preferably any one or a combination of at least two of acetate, hydrochloride, nitrate, sulfate, phosphate, bromide and corresponding hydrate of the corresponding metal element in the metal oxide, preferably hydrochloride.
In the preparation method of the invention, the reducing agent is selected from any one or a combination of at least two of sodium borohydride, urea, vitamin C, hydrazine hydrate, ammonia water and ethylenediamine, preferably ethylenediamine;
preferably, the reducing agent is 1-20 times, e.g. 3-6-9-12-15-18-preferably 2-10-times, the mass of graphene oxide.
In the preparation method of the invention, the ultrasonic mixing is carried out, and the ultrasonic frequency is 20-200KHz, such as 50KHz, 75KHz, 100KHz, 125KHz, 150KHz and 175KHz; the ultrasonic time is 0.5-2.5h, such as 0.8h, 1.1h, 1.4h, 1.7h, 2.0h, 2.3h;
The stirring speed is 300-600rpm, such as 350rpm, 400rpm, 450rpm, 500rpm, 550rpm; the stirring time is 2-5h, such as 2.5h, 3.0h, 3.5h, 4.0h, 4.5h.
In the preparation method of the invention, the reaction is preferably carried out in a polytetrafluoroethylene reaction kettle.
In the preparation method, the graphene oxide and metal ferrite raw materials are existing products, can be directly purchased from the market, and can also be prepared by any disclosed prior art, and the preparation method has no special requirements, for example, the graphene oxide is prepared by oxidizing by adopting a traditional Hummers method to obtain graphene oxide dispersion liquid; for example, the metal ferrite is prepared by adopting a coprecipitation method.
The invention also provides application of the catalyst in the field of electrochemical preparation of beta-carotene, and is particularly suitable for a method for preparing beta-carotene from vitamin A triphenylphosphine salt (C20 phosphine salt) through electrochemistry.
Preferably, the invention provides a method for electrochemically preparing beta-carotene from vitamin A triphenylphosphine salt, which comprises the steps of taking an aqueous solution of the vitamin A triphenylphosphine salt as an electrolyte, and carrying out electrolytic reaction in the presence of the catalyst and alkali to prepare the beta-carotene.
In the invention, the vitamin A triphenylphosphine salt (C20 phosphine salt) is a compound with a structure shown in a formula 1:
in the invention, the vitamin A triphenylphosphine salt (C20 phosphine salt) is an existing compound and can be prepared by any disclosed prior art, and the invention has no special requirement. The C20 phosphine salt shown in the formula 1 can be prepared by referring to the method of patent US3294844A, and the invention is not repeated.
In the invention, the alkali is selected from any one or a combination of at least two of sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, preferably sodium carbonate;
Preferably, the base is used after formulation with water as a lye having a concentration of 10-25wt%, e.g. 132wt%, 16wt%, 19wt%, 22wt%, preferably 15-20wt%;
Preferably, the alkali liquor is fed continuously, more preferably dropwise, for a period of 10-60min, for example 15min, 25min, 35min, 45min, 55min, preferably 20-40min, and the alkali liquor is fed for a period of time not counted in the electrolytic reaction time.
In the invention, the mass ratio of the vitamin A triphenylphosphine salt to water is 1:5-15, for example, 1: 7. 1: 9. 1: 11. 1:13, preferably 1:8-10.
In the present invention, the catalyst mass is 10-30%, such as 13%, 16%, 19%, 22%, 25%, 28%, preferably 15-20% of the vitamin A triphenylphosphine salt mass.
In the present invention, the molar ratio of the vitamin A triphenylphosphine salt to the base is 1:1-2.5, e.g. 1:1.3, 1:1.6, 1:1.9, 1:2.2, preferably 1:1.1-2.
In the present invention, the electrolytic reaction has a current density of 300 to 800A/m 2, for example 350A/m2、400A/m2、 450A/m2、500A/m2、550A/m2、600A/m2、650A/m2、700A/m2、750A/m2,, preferably 500 to 600A/m 2; the reaction temperature is 10-40deg.C, such as 15deg.C, 20deg.C, 25deg.C, 30deg.C, 35deg.C, preferably 20-30deg.C; the reaction time is 1 to 5 hours, for example 1.5 hours, 2.5 hours, 3.5 hours, 4.5 hours, preferably 2 to 3 hours.
In the invention, the electrolytic reaction is carried out in a diaphragm-free electrolytic cell, and the cathode electrode and the anode electrode of the diaphragm-free electrolytic cell are selected from one or more of inert electrodes, preferably platinum electrodes, gold electrodes and graphite electrodes.
After the electrolytic reaction is finished, the invention further comprises post-treatment processes such as catalyst recovery, separation, drying and the like.
Wherein, the method for recovering the catalyst comprises the following steps: the catalyst is separated by an externally applied magnetic field, then is washed by dichloromethane (preferably 3-5 times), and can be used after being dried, the application time can reach at least 10 times, and the reaction yield has no obvious change (the yield is reduced by not more than 0.5%).
The separation and drying are conventional operations in the field, the method is not particularly required, and in some specific examples, the method preferably adopted by the invention is that the electrolytic reaction solution after catalyst recovery is filtered, and the solid is washed with water and dried to obtain the beta-carotene.
Preferably, in the invention, the filtrate after the filtration of the electrolytic reaction liquid can be continuously recycled to the next electrolytic reaction, when the filtrate is recycled, sulfuric acid is added to adjust the PH to be neutral, then the filtrate is concentrated to remove the water introduced by alkali liquor, and then the filtrate is transferred to an electrolytic tank for recycling, when the filtrate is recycled, each raw material is added to the required dosage, the recycling time can reach at least 10 times, and the reaction yield is not obviously changed (the yield is reduced by not more than 0.3%).
Analysis the principle of the reaction of the C20 electrochemical reaction of the present invention to produce beta-carotene may be represented as follows:
Anode:
And (3) cathode:
4H2O+4e-→4OH-+2H2
In the electrolyte, the C20 phosphine salt firstly reacts with alkali liquor to generate an intermediate containing C=P, and the intermediate is partially oxidized under the action of anode generated oxygen to generate C20 aldehyde, and then reacts with the intermediate to generate beta-carotene. The alkali liquor can react with the C20 phosphine salt to initiate reaction, and can increase the conductivity of water and increase the oxygen production rate of electrolysis.
In the preparation process of the catalyst, graphene oxide, a metal oxide precursor (metal salt) and a reducing agent reduce graphene oxide under hydrothermal conditions, oxygen atoms and metal salt generate metal oxide to grow on a reduced graphene sheet layer, the reduced graphene serves as a catalyst carrier, and metal ferrite and metal oxide are fully dispersed and loaded on the carrier. The oxide can be combined with oxygen generated by the electrolysis reaction to form an oxidation intermediate with stronger oxidability, and the intermediate of C=P is oxidized to promote the reaction. The presence of the ferrate in the catalyst can stabilize the intermediate formed by the catalyst and oxygen on the one hand, and can make the catalyst magnetic on the other hand, and after the reaction is finished, the catalyst can be separated from the electrolyte and the generated insoluble solid organic matters through magnetism, so that the catalyst can be recovered and reused.
In addition, in the present invention, the produced organic matter is hardly soluble in water except the catalyst, and after magnetically separating the catalyst, the beta-carotene product can be separated by simple filtration. The filtrate can be used as the electrolyte of the next batch after adjusting the pH and concentrating part of water.
Compared with the prior art, the method has the beneficial effects that:
The invention adopts an electrochemical method, avoids the use of an oxidant in the traditional process, has the advantages of environmental protection, strong safety, high yield of the product beta-carotene (more than 90 percent), recycling of the catalyst and electrolyte, small waste water amount and the like compared with the existing electrochemical method.
Detailed Description
The following further describes the technical scheme of the present invention, but is not limited thereto, and all modifications and equivalents of the technical scheme of the present invention are included in the scope of the present invention without departing from the scope of the technical scheme of the present invention.
The main raw material source information in the embodiment of the invention is as follows, and other raw materials are common commercial raw materials unless specified otherwise:
Vitamin a triphenylphosphine salt (C20 phosphine salt): reference US3294844a method, the specific steps are: 32.8g of vitamin A acetate, 9.8g of sulfuric acid, 26.2g of triphenylphosphine and 250ml of methanol are mixed and stirred at room temperature for reaction for 8 hours. After the reaction is finished, concentrating the solvent under reduced pressure, adding 100ml of acetonitrile into the residual concentrate, cooling to-10 ℃, stirring for 3 hours, filtering, and drying the solid to obtain the C20 phosphine salt.
Graphene oxide: shanghai Yuan Ye Biotechnology Co., ltd., product number S24800;
metallic ferrite was purchased from the Amara Ding Shiji net.
Liquid chromatography conditions: chromatographic model: agilent 1260; chromatographic column: c30 column YMC carotenoid S-5um (4.6. Times.250 nm); mobile phase: a: acetonitrile, B: isopropyl alcohol; column temperature: 40 ℃; flow rate: 1.0mL/min; sample injection amount: 10. Mu.L; detection wavelength: 455nm.
Example 1
Preparation of catalyst a:
Mixing 20g of graphene oxide with 2000g of water to obtain graphene oxide dispersion, mixing the graphene oxide dispersion with 1g of NiFe 2O4, performing ultrasonic treatment at 100KHz for 1h, adding 13.16g of cobalt acetate tetrahydrate (corresponding to the mass of cobalt oxide of 3.96 g), 160g of ethylenediamine, fully stirring at 500rpm for 3h, transferring into a reaction kettle of a polytetrafluoroethylene liner, and reacting at 200 ℃ for 12h. And after the reaction is finished, magnetically separating the solid, washing the solid three times with 40g of deionized water each time, and drying the solid to obtain the catalyst a.
XPS was used to determine catalyst composition: based on the mass of the graphene carrier, the loading of nickel ferrite is 5wt% and the loading of cobalt oxide is 18wt%.
Example 2
Preparation of catalyst b:
mixing 20g of graphene oxide with 2000g of water to obtain graphene oxide dispersion liquid, mixing the graphene oxide dispersion liquid with 2.0 gCoFe 2O4 g of water, performing ultrasonic treatment at 20KHz for 2.5h, adding 8.61g of stannous chloride dihydrate (corresponding to the mass of the stannic oxide being 5.75 g), adding 20g of hydrazine hydrate, stirring for 5h at 300rpm, transferring into a reaction kettle of a polytetrafluoroethylene liner, and reacting at 220 ℃ for 10h. And after the reaction is finished, carrying out solid magnetic separation, washing three times with 50g of deionized water each time, and drying the solid to obtain the catalyst b.
XPS was used to determine catalyst composition: based on the mass of the graphene carrier, the loading of cobalt ferrite is 10wt% and the loading of tin oxide is 25wt%.
Example 3
Preparation of catalyst c:
Mixing 20g of graphene oxide with 2000g of water to obtain graphene oxide dispersion liquid, mixing the graphene oxide dispersion liquid with 0.8g of CuFe 2O4, performing ultrasonic treatment at 200KHz for 0.5h, adding 3.17g of yttrium chloride hexahydrate (corresponding to the mass of yttrium oxide being 2.36 g), fully stirring for 2h at 600rpm, transferring into a reaction kettle of a polytetrafluoroethylene liner, and reacting at 150 ℃ for 18h. And after the reaction is finished, magnetically separating the solid, washing the solid three times with 25g of deionized water each time, and drying the solid to obtain the catalyst c.
XPS was used to determine catalyst composition: based on the mass of the graphene carrier, the loading of copper ferrite is 4wt% and the loading of yttrium oxide is 10wt%.
Example 4
12.58G of C20 phosphine salt (0.02 mol), 1.89g (15%) of catalyst a and 100.6g of water were taken in an electrolytic cell, the temperature was kept at 25℃and the voltage was adjusted so that the current density became 600A/m 2, 12.72g of 20wt% aqueous Na 2CO3 solution (Na 2CO3 2.54g,0.02 mol) was added dropwise over a period of 10 minutes. After the completion of the dropwise addition, the reaction was carried out for 3 hours. After the reaction is finished, magnetically separating and recovering the catalyst, filtering the electrolyte, washing the solid with water, and drying to obtain the beta-carotene product.
The conversion of the beta-carotene product after dissolution in methylene chloride was 100%, the selectivity was 90.4% and the beta-carotene yield was 90.4%.
The filtrate obtained by filtering the electrolytic reaction solution was neutralized to ph=7 with sulfuric acid, concentrated under reduced pressure to obtain 10.18g of water (water contained in Na 2CO3 solution), poured into an electrolytic cell, and mixed with the raw materials such as C20 phosphine salt in the above-mentioned raw material ratio according to this example, and subjected to electrolysis under the reaction conditions according to this example. The experimental results are shown in Table 1 below (the conversion of the reaction can reach 100% because the C20 phosphine salt is almost impossible under alkaline conditions, and the conversion of the reaction in the following examples is 100%):
TABLE 1 data for electrolyte application
Number of times of application 0 1 3 5 7 10
Yield/% 90.4 90.4 90.4 90.3 90.3 90.2
The catalyst separated by the external magnetic field is washed 3-5 times by methylene dichloride, dried and then electrolyzed and reused according to the proportion of the raw materials and the reaction conditions in the embodiment. The experimental results data are set forth in table 2 below:
table 2 data for catalyst set
Number of times of application 0 1 3 5 7 10
Yield/% 90.4 90.4 90.3 90.3 90.2 90.0
Example 5
12.58G of C20 phosphine salt (0.02 mol), 1.64g (13%) of catalyst b and 188.7g of water are taken in an electrolytic cell, the temperature is kept at 35℃and the voltage is adjusted to a current density of 800A/m 2, 13.33g of 15% strength by weight aqueous NaOH solution (2.0 g,0.05 mol) are added dropwise, and the dropwise addition time is 60 minutes. After the completion of the dropwise addition, the reaction was carried out for 1.5 hours. After the reaction is finished, magnetically separating and recovering the catalyst, filtering the electrolyte, washing the solid with water, and drying to obtain the beta-carotene product.
The conversion of the beta-carotene product after dissolution in methylene chloride was 100%, the selectivity was 90.1% and the beta-carotene yield was 90.1%.
The filtrate obtained by filtering the electrolytic reaction solution was neutralized to ph=7 with sulfuric acid, concentrated under reduced pressure to obtain 11.3g of water (water contained in NaOH solution), poured into an electrolytic cell, and mixed with the raw materials such as C20 phosphine salt in the above-mentioned raw material ratio of this example, and subjected to electrolysis under the reaction conditions of this example. The experimental results data are set forth in table 3 below:
TABLE 3 data for electrolyte application
Number of times of application 0 1 3 5 7 10
Yield/% 90.1 90.1 90.0 90.0 90.0 89.9
The catalyst separated by the external magnetic field is washed 3-5 times by methylene dichloride, dried and then electrolyzed and reused according to the proportion of the raw materials and the reaction conditions in the embodiment. The experimental results data are set forth in table 4 below:
table 4 data for catalyst set
Number of times of application 0 1 3 5 7 10
Yield/% 90.1 90.1 90.0 89.9 89.8 89.7
Example 6
12.58G of C20 phosphine salt (0.02 mol), 3.77g (30%) of catalyst c and 65.0g of water are taken in an electrolytic cell, the temperature is kept at 15℃and the voltage is adjusted so that the current density is 350A/m 2, 41.40g of 10% strength by weight aqueous K 2CO3 solution (K 2CO3 4.1.1 g,0.03 mol) are added dropwise for 30min. After the completion of the dropwise addition, the reaction was carried out for 5 hours by electrolysis. After the reaction is finished, magnetically separating and recovering the catalyst, filtering the electrolyte, washing the solid with water, and drying to obtain the beta-carotene product.
The conversion of the beta-carotene product after dissolution in methylene chloride was 100%, the selectivity was 89.8% and the beta-carotene yield was 89.8%.
The filtrate obtained by filtering the electrolytic reaction solution was neutralized to ph=7 with sulfuric acid, concentrated under reduced pressure to obtain 37.26g of water (water contained in the K 2CO3 solution), poured into an electrolytic cell, and mixed with the raw materials such as C20 phosphine salt in the above-mentioned raw material ratio of this example, and subjected to electrolysis under the reaction conditions of this example. The experimental results data are set forth in table 5 below:
TABLE 5 data for electrolyte application
Number of times of application 0 1 3 5 7 10
Yield/% 89.8 89.8 89.7 89.7 89.6 89.5
The catalyst separated by the external magnetic field is washed 3-5 times by methylene dichloride, dried and then electrolyzed and reused according to the proportion of the raw materials and the reaction conditions in the embodiment. The experimental results data are set forth in table 6 below:
TABLE 6 data for catalyst sleeve
Number of times of application 0 1 3 5 7 10
Yield/% 89.8 89.8 89.7 89.6 89.5 89.3
Comparative example 1
The procedure of example 4 was followed except that no catalyst was added, the reaction conversion was 100%, and the yield of beta-carotene was 31.0%.
Comparative example 2
The catalyst was prepared according to the procedure of example 1, except that no metal oxide precursor (cobalt acetate tetrahydrate) was added during the preparation, designated comparative catalyst a. Comparative catalyst a was examined by the method of example 4, and the reaction conversion was 100% and the beta-carotene yield was 33.2%.
Comparative example 3
The catalyst was prepared according to the procedure of example 1, except that no metallic ferrite (NiFe 2O4) was added during the preparation, designated comparative catalyst b. Comparative catalyst b was examined by the method of example 4, and the reaction conversion was 100% and the yield of beta-carotene was 58.5%.
Comparative example 4
A catalyst was prepared according to the method of example 1, except that graphene oxide was replaced with equal mass of activated carbon, denoted as comparative catalyst c. Comparative catalyst b was examined by the method of example 4, and the reaction conversion was 100% and the beta-carotene yield was 64.3%.
Comparative example 5
The catalyst was prepared according to the procedure of example 1, except that the metallic ferrite (NiFe 2O4) was replaced with zinc tungstate of equal mass, designated comparative catalyst d. Comparative catalyst b was examined by the method of example 4, and the reaction conversion was 100% and the beta-carotene yield was 60.1%.
Comparative example 6
The catalyst was prepared according to the procedure of example 1, except that the metal oxide precursor (cobalt acetate tetrahydrate) was replaced with an equal mass of copper sulphide, denoted comparative catalyst e. Comparative catalyst b was examined by the method of example 4, and the reaction conversion was 100% and the beta-carotene yield was 31.8%.
The above embodiments are not intended to limit the technical solution of the present invention in any way. Any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention fall within the protection scope of the present invention.

Claims (24)

1. The method is characterized in that an aqueous solution of the vitamin A triphenylphosphine salt is used as an electrolyte, and the beta-carotene is prepared by carrying out electrolytic reaction in the presence of a catalyst and alkali;
The catalyst is a graphene-supported metal ferrite and metal oxide catalyst, wherein the loading amount of the metal ferrite is 4-10wt% and the loading amount of the metal oxide is 10-25wt% based on the mass of the graphene carrier;
The metal ferrite is selected from any one or a combination of at least two of manganese ferrite, cobalt ferrite, zinc ferrite, nickel ferrite and copper ferrite; the metal oxide is selected from any one or a combination of at least two of titanium oxide, chromium oxide, cobalt oxide, manganese dioxide, nickel oxide, copper oxide, zinc oxide, yttrium oxide and zirconium oxide.
2. The method according to claim 1, wherein the loading of the metallic ferrite is 5-7wt% and the loading of the metallic oxide is 15-20wt%.
3. The method according to claim 1, wherein the method for preparing the catalyst comprises the steps of: mixing graphene oxide with water to obtain graphene oxide dispersion liquid, then mixing the graphene oxide dispersion liquid with metal ferrite in an ultrasonic manner, adding a metal oxide precursor and a reducing agent into the mixture, fully stirring the mixture, performing hydrothermal reaction at 150-220 ℃ for 10-18h, washing with water after the reaction is completed, and drying to obtain the catalyst.
4. A method according to claim 3, wherein the hydrothermal reaction is carried out at a temperature of 180-200 ℃ for a period of 12-15 hours.
5. A method according to claim 3, wherein the graphene oxide dispersion has a mass of water of 100-300 times the mass of graphene oxide; and/or
The mass of the metal ferrite is 4-10% of that of the graphene oxide; and/or
The mass of the metal oxide obtained by the metal oxide precursor is 10-30% of that of graphene oxide;
The metal oxide precursor is selected from metal soluble salts; and/or
The reducing agent is selected from any one or a combination of at least two of sodium borohydride, urea, vitamin C, hydrazine hydrate, ammonia water and ethylenediamine;
The mass of the reducing agent is 1-20 times of that of the graphene oxide; and/or
The ultrasonic mixing is carried out, and the ultrasonic frequency is 20-200KHz; the ultrasonic time is 0.5-2.5h; and/or
The stirring is carried out fully, and the stirring speed is 300-600rpm; the stirring time is 2-5h.
6. The method of claim 5, wherein the graphene oxide dispersion has a mass of water that is 200-250 times the mass of graphene oxide.
7. The method of claim 5, wherein the metal ferrite mass is 5-7% of the graphene oxide mass.
8. The method of claim 5, wherein the metal oxide precursor corresponds to a metal oxide mass of 15-20% of the mass of graphene oxide.
9. The method of claim 5, wherein the metal soluble salt is any one or a combination of at least two of acetate, hydrochloride, nitrate, sulfate, phosphate, bromide, and corresponding hydrate of the corresponding metal element in the metal oxide.
10. The method of claim 7, wherein the reducing agent is 2-10 times the mass of graphene oxide.
11. The method of claim 1, wherein the vitamin a triphenylphosphine salt is a compound having a structure represented by formula 1:
and/or
The alkali is selected from any one or a combination of at least two of sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate; and/or
In the aqueous solution of the vitamin A triphenylphosphine salt, the mass ratio of the vitamin A triphenylphosphine salt to water is 1:5-15; and/or
The mass of the catalyst is 10-30% of the mass of the vitamin A triphenylphosphine salt; and/or
The molar ratio of the vitamin A triphenylphosphine salt to the alkali is 1:1-2.5.
12. The method of claim 11, wherein the mass ratio of the vitamin a triphenylphosphine salt to water in the aqueous solution of the vitamin a triphenylphosphine salt is 1:8-10.
13. The method according to claim 11, wherein the catalyst mass is 15-20% of the vitamin a triphenylphosphine salt mass.
14. The method of claim 11, wherein the molar ratio of the triphenylphosphine salt to base of vitamin a is 1:1.1-2.
15. The method according to claim 1, wherein the alkali is used after the alkali and water are formulated into alkali liquor, and the alkali liquor concentration is 10-25wt%.
16. The method according to claim 15, wherein the alkali is used after the alkali and water are formulated as an alkali solution, and the alkali solution concentration is 15-20wt%.
17. The method according to claim 15, wherein the lye is fed continuously for a period of 10-60min, and the lye is fed for a period of time which does not account for the electrolytic reaction time.
18. The method of claim 17, wherein the feed time is 20-40 minutes.
19. The method according to claim 17, wherein the lye is added dropwise.
20. The method according to claim 1, wherein the electrolytic reaction has a current density of 300-800A/m 2, a reaction temperature of 10-40 ℃ and a reaction time of 1-5h.
21. The method of claim 20, wherein the electrolytic reaction has a current density of 500-600A/m 2, a reaction temperature of 20-30 ℃ and a reaction time of 2-3h.
22. The method of claim 1, wherein the electrolytic reaction is carried out in a diaphragm-free electrolytic cell, the cathode electrode and the anode electrode of the diaphragm-free electrolytic cell being selected from inert electrodes.
23. The method of claim 22, wherein the cathode electrode and the anode electrode of the diaphragm-free electrolyzer are each selected from one or more of a platinum electrode, a gold electrode, and a graphite electrode.
24. The method according to claim 1, wherein after the electrolytic reaction is completed, the catalyst is separated by an externally applied magnetic field, then washed with dichloromethane, dried and then applied;
Filtering the electrolytic reaction solution after recovering the catalyst, washing the solid with water, and drying to obtain beta-carotene;
The filtered filtrate is circularly used in the next electrolytic reaction, when in use, sulfuric acid is added to the filtrate to adjust the pH value to be neutral, then the filtrate is concentrated to remove the water introduced by alkali liquor, and then the filtrate is transferred into an electrolytic tank for use, and when in use, all raw materials are added to the required dosage.
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