CN114534729A - Catalyst, preparation method thereof and application thereof in preparing beta-carotene by electrochemical method - Google Patents

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

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CN114534729A
CN114534729A CN202210213963.4A CN202210213963A CN114534729A CN 114534729 A CN114534729 A CN 114534729A CN 202210213963 A CN202210213963 A CN 202210213963A CN 114534729 A CN114534729 A CN 114534729A
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catalyst
oxide
metal
carotene
ferrite
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CN114534729B (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-loaded metal ferrite and metal oxide catalyst. The water solution of vitamin A triphenylphosphine salt is used as electrolyte, and the beta-carotene is prepared by electrolytic reaction in the presence of the catalyst and alkali. The method disclosed by the invention is high in product yield, avoids the use of an oxidant in the traditional process, is high in safety, and is green and environment-friendly. The method also has the advantages of high yield (more than 90 percent) of the beta-carotene product, recyclable catalyst and electrolyte, small amount of waste water and the like.

Description

Catalyst, preparation method thereof and application thereof in preparing 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 preparation of beta-carotene by an electrochemical method.
Background
beta-Carotene (beta-Carotene, molecular formula C)40H56The structure is shown as the following formula) is an antioxidant, has the detoxification function, is an indispensable nutrient for maintaining human health, is widely applied to industries such as medicine, food, cosmetics, feed additives, dye and the like, and has good market prospect.
Figure BDA0003533679130000011
There are presently disclosed processes for preparing beta-carotene from vitamin A and derivatives thereof, including Bernhard Schulz et al (Bernhard Schulz, et al, U.S. Pat. No. 4,105,855, Manual of symmetric Carotenoids, [ P ]1978), which provide a process for obtaining beta-carotene by reacting a C20 phosphonium salt in the presence of a base and a peroxide to produce a solid, and isomerizing the solid by extraction, washing, solvent removal, etc.
The method has low yield, and the peroxide used in the reaction process can oxidize beta-carotene, and has high safety risk.
CN101081829A discloses a method for preparing beta-carotene by oxidizing C20 phosphine salt under the condition of two phases of water and a water-insoluble solvent, wherein the generated beta-carotene is extracted into an organic phase, thereby avoiding oxidation by an aqueous phase oxidant. The method has the same low yield, and simultaneously needs a large amount of solvent for dissolution because the solubility of the beta-carotene in the organic solvent is relatively low, and simultaneously, the method also generates a large amount of waste water to be treated, which is not beneficial to industrial amplification, and in addition, the existence of the oxidant also has the safety risk.
The method disclosed in CN101041631A adopts sodium hypochlorite as the oxidant, which improves the safety of the oxidant, but the reaction is also performed under a two-phase condition, and the yield is low, only about 40%.
CN110452147A discloses a method of using molecular oxygen as an oxidant, and adding a palladium catalyst and a cyclodextrin substance as a phase transfer catalyst. The method has high yield, but needs to be carried out under high pressure, has certain safety risk, and simultaneously, the use of water and an organic solvent also causes the problem that a large amount of wastewater needs to be treated.
CN107653459A discloses a method for preparing beta-carotene by oxidizing C20 phosphonium salt by electrochemical method. The method uses the electrolyzed water to generate oxygen for oxidation, avoids the use of the traditional oxidant, reduces the reaction risk, and simultaneously has more green and environment-friendly route. However, the method has the problems of high alkali consumption, low reaction yield and insufficient oxygen utilization.
In conclusion, in the prior art, the disclosed processes for preparing beta-carotene by oxidative coupling of C20 phosphonium salt still have the problems of low reaction yield, certain safety risk in the use of oxidant and large amount of waste water generated after reaction. Therefore, it is required to develop a novel method for producing beta-carotene that can solve the above problems.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a catalyst, which can be used in a method for electrochemically preparing β -carotene from vitamin a triphenylphosphine salt (C20 phosphine salt), and a preparation method thereof. The electrochemical method disclosed by the invention avoids the use of an oxidant in the traditional process, is high in safety, green and environment-friendly, and has the advantages of high product yield, recyclable catalyst and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a catalyst which can be used for electrochemically preparing beta-carotene, in particular a graphene-loaded metal ferrite and metal oxide catalyst, wherein based on the mass of a graphene carrier,
the loading of the metal ferrite is 4 to 10% by weight, for example 4.5%, 5.5%, 6.5%, 7.5%, 8.5%, 9.5%, preferably 5 to 7%;
the loading of the metal oxide is 10 to 25 wt%, for example 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, 22 wt%, preferably 15 to 20 wt%.
In the present invention, the metal ferrite is selected from the group consisting of ferrites of the fourth cycle transition metals, including 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 the group consisting of fourth and fifth cycle transition metal oxides, including 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) Zirconium oxide (ZrO)2) Any one or a combination of at least two of them, 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 a graphene oxide dispersion, then ultrasonically mixing the graphene oxide dispersion with metal ferrite, adding a metal oxide precursor and a reducing agent into the graphene oxide dispersion, fully stirring, carrying out hydrothermal reaction at the temperature of 150-220 ℃, such as 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, preferably 180-200 ℃ for 10-18h, such as 11h, 12h, 13h, 14h, 15h, 16h, 17h, preferably 12-15h, and washing and drying after the reaction is finished to obtain the catalyst.
In the preparation method of the invention, the mass of the graphene oxide dispersion liquid is 300 times, such as 125 times, 150 times, 175 times, 200 times, 225 times, 250 times, 275 times, preferably 200 times, 250 times, the mass of the water is 100 times, 300 times, 125 times, 150 times, 175 times, 200 times, 225 times, 250 times, 275 times, preferably 200 times, 250 times, the mass of the water is one time.
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%, preferably 5-7%; said metal ferrite corresponds to the metal ferrite of the aforementioned catalyst, i.e. a ferrite selected from the group consisting of the fourth cycle transition metals.
In the preparation method of the present invention, the mass of the metal oxide obtained by the metal oxide precursor is 10 to 30% of the mass of the graphene oxide, for example, 12.5%, 15.0%, 17.5%, 20.0%, 22.5%, 25.0%, 27.5%, preferably 15 to 20%;
preferably, the metal oxide precursor is selected from metal soluble salts, wherein the metal element in the metal soluble salts corresponds to the metal element contained in the metal oxide in the catalyst, i.e. is 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, and is preferably hydrochloride.
In the preparation method, 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, and preferably ethylenediamine;
preferably, the mass of the reducing agent is 1 to 20 times, for example, 3 times, 6 times, 9 times, 12 times, 15 times, 18 times, preferably 2 to 10 times that of graphene oxide.
In the preparation method, the ultrasonic frequency is 20-200KHz, such as 50KHz, 75KHz, 100KHz, 125KHz, 150KHz and 175 KHz; the ultrasonic time is 0.5-2.5h, such as 0.8h, 1.1h, 1.4h, 1.7h, 2.0h and 2.3 h;
the stirring speed is 300-600rpm, such as 350rpm, 400rpm, 450rpm, 500rpm and 550 rpm; the stirring time is 2-5h, such as 2.5h, 3.0h, 3.5h, 4.0h, 4.5 h.
In the preparation method of the present invention, the reaction is preferably performed in a reaction vessel made of polytetrafluoroethylene.
In the preparation method, the graphene oxide and the metal ferrite are existing products, can be directly purchased from the market, and can also be prepared by any published existing technology, and the preparation method has no special requirements, for example, the graphene oxide is prepared by the traditional Hummers method to obtain the graphene oxide dispersion liquid; for example, a coprecipitation method is used to prepare metal ferrite.
The invention also provides application of the catalyst in the field of electrochemical preparation of beta-carotene, and particularly provides 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 takes an aqueous solution of the vitamin A triphenylphosphine salt as an electrolyte and carries out electrolytic reaction in the presence of the catalyst and alkali, thus preparing 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:
Figure BDA0003533679130000051
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 phosphonium salt shown in 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, and is preferably sodium carbonate;
preferably, the alkali is used after being formulated with water as a lye, the lye having a concentration of 10 to 25 wt.%, for example 132 wt.%, 16 wt.%, 19 wt.%, 22 wt.%, preferably 15 to 20 wt.%;
preferably, the alkali liquor is continuously added, more preferably dropwise added, for 10-60min, such as 15min, 25min, 35min, 45min, 55min, preferably 20-40min, and the alkali liquor addition time is not counted in the electrolysis reaction time.
In the invention, the mass ratio of the vitamin A triphenylphosphine salt to water is 1:5-15, such as 1: 7. 1: 9. 1: 11. 1: 13, preferably 1: 8-10.
In the present invention, the mass of the catalyst is 10 to 30% of the mass of the vitamin A triphenylphosphine salt, for example, 13%, 16%, 19%, 22%, 25%, 28%, preferably 15 to 20%.
In the present invention, the molar ratio of the vitamin a triphenylphosphine salt to the base is 1:1-2.5, for example 1: 1.3, 1: 1.6, 1: 1.9, 1: 2.2, preferably 1: 1.1-2.
In the invention, the current density of the electrolytic reaction is 300-800A/m2E.g. 350A/m2、400A/m2、 450A/m2、500A/m2、550A/m2、600A/m2、650A/m2、700A/m2、750A/m2Preferably 500-600A/m2(ii) a The reaction temperature is 10-40 deg.C, such as 15 deg.C, 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, preferably 20-30 deg.C; the reaction time is from 1 to 5 hours, for example from 1.5 hours, 2.5 hours, 3.5 hours, 4.5 hours, preferably from 2 to 3 hours.
In the invention, the electrolytic reaction is carried out in a diaphragm-free electrolytic cell, and a cathode electrode and an anode electrode of the diaphragm-free electrolytic cell are both selected from inert electrodes, preferably one or more of a platinum electrode, a gold electrode and a graphite electrode.
After the electrolysis reaction is finished, the method also comprises the post-treatment processes of catalyst recovery, separation, drying and the like.
Wherein the method for recovering the catalyst comprises the following steps: the catalyst is separated by an external magnetic field, then is washed by dichloromethane (preferably 3-5 times), and can be reused after being dried, the reuse 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 invention has no special requirement, and in some specific examples, the invention preferably adopts a method that firstly the electrolytic reaction liquid after the catalyst is recovered is filtered, and the solid is washed by water and dried to obtain the beta-carotene.
Preferably, in the invention, the filtrate obtained after the filtration of the electrolytic reaction solution can be continuously and circularly applied to the next electrolytic reaction, when the filtrate is applied, sulfuric acid is added into the filtrate to adjust the pH value to be neutral, the water introduced by the alkali liquor is concentrated and removed, then the filtrate is transferred into an electrolytic cell to be applied, when the filtrate is applied, all the raw materials are added to the required dosage, the application frequency can reach at least 10 times, and the reaction yield is not obviously changed (the yield is reduced by not more than 0.3%).
The reaction principle of the electrochemical reaction of C20 for preparing beta-carotene according to the present invention may be expressed as follows:
anode:
Figure BDA0003533679130000081
cathode:
4H2O+4e-→4OH-+2H2
in the electrolyte, C20 phosphonium salt firstly generates an intermediate containing C ═ P with alkali liquor, the intermediate is partially oxidized under the action of oxygen generated at the anode to generate C20 aldehyde, and then reacts with the intermediate to generate beta-carotene. The existence of the alkali liquor can not only react with C20 phosphonium salt to initiate reaction, but also increase the conductivity of water and improve the rate of oxygen production by electrolysis.
In the preparation process of the catalyst, graphene oxide, a metal oxide precursor (metal salt) and a reducing agent are subjected to reduction under a hydrothermal condition, meanwhile, oxygen atoms and the metal salt generate metal oxide to grow on a reduced graphene sheet layer, the reduced graphene serves as a catalyst carrier, and meanwhile, metal ferrite and the 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 oxidizability, and the oxidation of the intermediate of C ═ P is carried out to promote the reaction. The existence of ferrite in the catalyst can stabilize the intermediate formed by the catalyst and oxygen on one hand, and can enable the catalyst to have magnetism on the other hand, and after the reaction is finished, the catalyst can be separated from electrolyte and generated insoluble solid organic matters through magnetism, so that the recovery and reuse of the catalyst are realized.
In addition, in the invention, except the catalyst, the generated organic matters are almost insoluble in water, and after the catalyst is magnetically separated, the beta-carotene product can be separated by simple filtration. After the pH of the filtrate is adjusted and part of water is concentrated, the filtrate can be used as electrolyte of the next batch.
Compared with the prior art, the method has the advantages that:
the method adopts an electrochemical method, avoids the use of an oxidant in the traditional process, has an environment-friendly route and strong safety, and simultaneously has the advantages of high yield (more than 90 percent) of the product beta-carotene, recyclable catalyst and electrolyte, small amount of waste water and the like compared with the existing electrochemical method.
Detailed Description
The technical solutions of the present invention are further described below, but not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the scope of the technical solutions of the present invention.
The source information of the main raw materials in the examples of the present invention is as follows, and other raw materials are common commercial raw materials unless otherwise specified:
vitamin a triphenylphosphine salt (C20 phosphine salt): referring to the preparation method of US3294844A, the method comprises the following specific steps: vitamin A acetate (32.8 g), sulfuric acid (9.8 g), triphenylphosphine (26.2 g) and methanol (250 ml) were mixed and reacted with stirring at room temperature for 8 hours. After the reaction is finished, the solvent is concentrated under reduced pressure, 100ml of acetonitrile is added into the residual concentrate, the temperature is reduced to minus 10 ℃, the mixture is stirred for 3 hours, and the C20 phosphonium salt is obtained after filtering and solid drying.
And (3) graphene oxide: shanghai Yuan leaf Biotechnology Co., Ltd., Cat # S24800;
metallic ferrites were purchased from alatin reagent nets.
Liquid chromatography conditions: the chromatographic type is as follows: agilent 1260; a chromatographic column: c30 column YMC carotenoid S-5um (4.6 x 250 nm); mobile phase: a: acetonitrile, B: isopropyl alcohol; column temperature: 40 ℃; flow rate: 1.0 mL/min; sample introduction amount: 10 mu L of the solution; detection wavelength: 455 nm.
Example 1
Preparation of catalyst a:
mixing 20g of graphene oxide with 2000g of water to obtain graphene oxide dispersion, and then mixing the graphene oxide dispersion with 1g of NiFe2O4Mixing, performing ultrasonic treatment at 100KHz for 1h, adding 13.16g of cobalt acetate tetrahydrate (corresponding to the mass of cobalt oxide being 3.96g) and 160g of ethylenediamine, stirring at 500rpm for 3h, transferring into a reaction kettle with a polytetrafluoroethylene liner, and reacting at 200 ℃ for 12 h. And (3) magnetically separating the solid after the reaction is finished, washing the solid for three times by 40g of deionized water each time, and drying the solid to obtain the catalyst a.
The catalyst composition was determined using XPS: based on the mass of the graphene carrier, the loading capacity of nickel ferrite is 5 wt%, and the loading capacity of cobalt oxide is 18 wt%.
Example 2
Preparation of catalyst b:
mixing 20g of graphene oxide with 2000g of water to obtain graphene oxide dispersion, and mixing with 2.0g of CoFe2O4Mixing, performing ultrasonic treatment at 20KHz for 2.5h, adding 8.61g of stannous chloride dihydrate (corresponding to 5.75g of stannic oxide), 20g of hydrazine hydrate, stirring at 300rpm for 5h, transferring into a reaction kettle with a polytetrafluoroethylene inner container, and reacting at 220 ℃ for 10 h. And (3) magnetically separating the solid after the reaction is finished, washing the solid for three times by 50g of deionized water each time, and drying the solid to obtain the catalyst b.
The catalyst composition was determined using XPS: based on the mass of the graphene carrier, the loading capacity of cobalt ferrite is 10 wt%, and the loading capacity of tin oxide is 25 wt%.
Example 3
Preparation of catalyst c:
mixing 20g of graphene oxide with 2000g of water to obtain graphene oxide dispersion, and then mixing with 0.8g of CuFe2O4Mixing, performing ultrasonic treatment at 200KHz for 0.5h, adding 3.17g of yttrium chloride hexahydrate (corresponding to the mass of yttrium oxide being 2.36g), 400g of vitamin C, stirring at 600rpm for 2h, transferring into a reaction kettle with a polytetrafluoroethylene inner container, and reacting at 150 ℃ for 18 h. And (3) magnetically separating the solid after the reaction is finished, washing the solid for three times by 25g of deionized water each time, and drying the solid to obtain the catalyst c.
The catalyst composition was determined using XPS: based on the mass of the graphene carrier, the loading capacity of copper ferrite is 4 wt%, and the loading capacity of yttrium oxide is 10 wt%.
Example 4
12.58g of 12.58g C20 phosphine salt (0.02mol), 1.89g (15%) of catalyst a and 100.6g of water are added into an electrolytic cell, the temperature is kept at 25 ℃, and the voltage is adjusted to make the current density be 600A/m212.72g of 20% strength by weight Na are added dropwise2CO3Aqueous solution (Na)2CO32.54g, 0.02mol), the dropping time is 10 min. After the end of the dropwise addition, the electrolytic reaction was carried out for 3 hours. After the reaction is finished, magnetically separating and recovering the catalyst, then filtering the electrolyte, and washing and drying the solid to obtain the beta-carotene product.
The conversion rate of the test reaction of the beta-carotene product after being dissolved by dichloromethane is 100 percent, the selectivity is 90.4 percent, and the yield of the beta-carotene is 90.4 percent.
The filtrate obtained by filtering the electrolytic reaction solution was neutralized with sulfuric acid to pH 7, and then concentrated under reduced pressure to give 10.18g of water (Na)2CO3Water content in the solution), pouring the solution into an electrolytic cell, adding C20 phosphonium salt and other raw materials according to the ratio of the raw materials in the embodiment, mixing, and performing electrolytic application according to the reaction conditions in the embodiment. The data of the results of the experiments are shown in the following table 1 (since the C20 phosphonium salt hardly exists under the alkaline condition, the reaction conversion rate can reach 100%, and the reaction conversion rates of the following examples are all 100%):
table 1 electrolyte application data
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 obtained by the magnetic field separation was washed with dichloromethane 3-5 times, dried, and then used for electrolysis in accordance with the above raw material ratio and reaction conditions. The data of the applied experiment results are shown in the following table 2:
table 2 catalyst application data
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 12.58g C20 phosphine salt (0.02mol), 1.64g (13%) of catalyst b and 188.7g of water are added into an electrolytic cell, the temperature is kept at 35 ℃, and the voltage is adjusted to ensure that the current density is 800A/m213.33g of a 15 wt% aqueous NaOH solution (NaOH 2.0g, 0.05mol) was added dropwise over a period of 60 min. After the end of the dropwise addition, the electrolytic reaction was carried out for 1.5 hours. After the reaction is finished, magnetically separating and recovering the catalyst, then filtering the electrolyte, and washing and drying the solid to obtain the beta-carotene product.
The conversion rate of the test reaction of the beta-carotene product after being dissolved by dichloromethane is 100 percent, the selectivity is 90.1 percent, and the yield of the beta-carotene is 90.1 percent.
The filtrate obtained after filtration of the electrolytic reaction solution was neutralized with sulfuric acid to PH 7, and then concentrated under reduced pressure to obtain 11.3g of water (water contained in NaOH solution), which was then poured into an electrolytic cell, mixed with the above-mentioned raw materials in the ratio of C20 phosphonium salt, and then subjected to electrolysis under the reaction conditions of this example. The application experiment result data are shown in the following table 3:
TABLE 3 electrolyte application data
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 obtained by the magnetic field separation was washed with dichloromethane 3-5 times, dried, and then used for electrolysis in accordance with the above raw material ratio and reaction conditions. The application test result data are shown in the following table 4:
table 4 catalyst application data
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 12.58g C20 phosphine salt (0.02mol), 3.77g (30%) of catalyst c and 65.0g of water are added into an electrolytic cell, the temperature is kept at 15 ℃, and the voltage is adjusted to ensure that the current density is 350A/m241.40g of 10 wt.% K in concentration were added dropwise2CO3Aqueous solution (K)2CO34.1g, 0.03mol), the dropping time is 30 min. After the end of the dropwise addition, the electrolytic reaction was carried out for 5 hours. After the reaction is finished, magnetically separating and recovering the catalyst, then filtering the electrolyte, and washing and drying the solid to obtain the beta-carotene product.
The conversion rate of the test reaction of the beta-carotene product after being dissolved by dichloromethane is 100 percent, the selectivity is 89.8 percent, and the yield of the beta-carotene is 89.8 percent.
The filtrate obtained by filtering the electrolytic reaction solution was neutralized with sulfuric acid to pH 7, and then concentrated under reduced pressure to obtain 37.26g of water (K)2CO3Water content of the solution) Then, the mixture was poured into an electrolytic cell, and the raw materials such as C20 phosphonium salt were added and mixed according to the above ratio, and then used for electrolysis under the reaction conditions of the present example. The application test result data are shown in the following table 5:
TABLE 5 electrolyte application data
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 obtained by the magnetic field separation was washed with dichloromethane 3-5 times, dried, and then used for electrolysis in accordance with the above raw material ratio and reaction conditions. The application test result data are shown in the following table 6:
table 6 catalyst use data
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
Referring to the process of example 4, except that no catalyst was added, the reaction conversion was 100%, and the yield of β -carotene was 31.0%.
Comparative example 2
The catalyst was prepared by reference to the procedure of example 1, except that no metal oxide precursor (cobalt acetate tetrahydrate) was added during the preparation, designated as comparative catalyst a. Examining the comparative catalyst a with reference to the procedure of example 4, the reaction conversion was 100% and the yield of beta-carotene was 33.2%.
Comparative example 3
Catalyst was prepared by referring to the method of example 1, except that no metal ferrite (NiFe) was added during the preparation2O4) Designated as comparative catalyst b. When the comparative catalyst b was examined by referring to the method of example 4, the reaction conversion was 100% and the yield of beta-carotene was 58.5%.
Comparative example 4
A catalyst was prepared with reference to the method of example 1, except that graphene oxide was replaced with an equal mass of activated carbon, which was designated as comparative catalyst c. When the comparative catalyst b was examined by referring to the method of example 4, the reaction conversion was 100% and the yield of beta-carotene was 64.3%.
Comparative example 5
A catalyst was prepared by referring to the method of example 1, except that metallic ferrite (NiFe) was used2O4) The catalyst was replaced by zinc tungstate of equal mass and designated as comparative catalyst d. Examining comparative catalyst b with reference to the procedure of example 4, the reaction conversion was 100% and the yield of beta-carotene was 60.1%.
Comparative example 6
A catalyst was prepared by reference to the procedure of example 1 except that the metal oxide precursor (cobalt acetate tetrahydrate) was replaced with an equal mass of copper sulfide as comparative catalyst e. When the comparative catalyst b was examined by referring to the method of example 4, the reaction conversion was 100% and the yield of β -carotene was 31.8%.
The above embodiments are not intended to limit the technical solutions of the present invention in any way. Any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention fall within the scope of the present invention.

Claims (10)

1. A catalyst, characterized in that the catalyst is a graphene-supported metal ferrite and metal oxide catalyst, wherein the loading amount of the metal ferrite is 4-10 wt%, preferably 5-7 wt% based on the mass of the graphene carrier; the loading of the metal oxide is 10 to 25 wt%, preferably 15 to 20 wt%.
2. The catalyst according to claim 1, characterized in that the metal ferrite is selected from the group consisting of ferrites of fourth cycle transition metals, preferably any one or a combination of at least two of manganese ferrite, cobalt ferrite, zinc ferrite, nickel ferrite, copper ferrite, more preferably nickel ferrite; and/or
The metal oxide is selected from fourth and fifth period transition metal oxides, preferably any one or 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, and more preferably cobalt oxide.
3. A method for preparing the catalyst of claim 1 or 2, comprising the steps of: mixing graphene oxide with water to obtain a 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 graphene oxide dispersion liquid, fully stirring, carrying out hydrothermal reaction at 220 ℃ and preferably at 200 ℃ for 10-18h and preferably 12-15h at 150-.
4. The preparation method according to claim 3, wherein the graphene oxide dispersion liquid contains water in an amount of 100-300 times, preferably 200-250 times, the mass of the graphene oxide; and/or
The mass of the metal ferrite is 4-10%, preferably 5-7% of that of the graphene oxide; and/or
The mass of the metal oxide obtained by the metal oxide precursor is 10-30%, preferably 15-20% of the mass of the graphene oxide;
preferably, the metal oxide precursor is selected from metal soluble salts, more preferably, the metal soluble salts are any one or a combination of at least two of acetate, hydrochloride, nitrate, sulfate, phosphate, bromide and corresponding hydrate of corresponding metal elements in the metal oxide, and further preferably, the hydrochloride; and/or
The reducing agent is selected from any one or the combination of at least two of sodium borohydride, urea, vitamin C, hydrazine hydrate, ammonia water and ethylenediamine, and the ethylenediamine is preferred;
preferably, the mass of the reducing agent is 1-20 times, preferably 2-10 times that of the graphene oxide; and/or
Mixing the ultrasonic waves, wherein the ultrasonic frequency is 20-200 KHz; the ultrasonic time is 0.5-2.5 h; and/or
The stirring is carried out fully, and the stirring speed is 300-600 rpm; the stirring time is 2-5 h.
5. Use of the catalyst according to claim 1 or 2 or of the catalyst prepared by the process according to claim 3 or 4 in the field of electrochemical preparation of beta-carotene, in particular in the electrochemical preparation of beta-carotene from vitamin a triphenylphosphine salts.
6. A method for electrochemically preparing beta-carotene from vitamin A triphenylphosphine salt, which is characterized in that an aqueous solution of vitamin A triphenylphosphine salt is used as an electrolyte, and an electrolytic reaction is carried out in the presence of the catalyst of claim 1 or 2 or the catalyst prepared by the method of claim 3 or 4 and alkali, so as to prepare the beta-carotene.
7. The method of claim 6, wherein the vitamin A triphenylphosphine salt is a compound having the structure shown in formula 1:
Figure FDA0003533679120000021
and/or
The alkali is selected from any one or the combination of at least two of sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, and is preferably sodium carbonate;
preferably, the alkali and water are prepared into alkali liquor for use, and the concentration of the alkali liquor is 10-25 wt%, preferably 15-20 wt%;
preferably, the alkali liquor is continuously fed, more preferably dropwise fed, the feeding time is 10-60min, preferably 20-40min, and the alkali liquor feeding time is not counted in the electrolysis reaction time; and/or
The mass ratio of the vitamin A triphenylphosphine salt to water is 1:5-15, preferably 1: 8-10; and/or
The mass of the catalyst is 10-30% of that of the vitamin A triphenylphosphine salt, preferably 15-20%; and/or
The molar ratio of the vitamin A triphenylphosphine salt to the alkali is 1:1-2.5, preferably 1: 1.1-2.
8. The method as claimed in claim 6 or 7, wherein the current density of the electrolysis reaction is 300-2Preferably 500-600A/m2(ii) a The reaction temperature is 10-40 ℃, preferably 20-30 ℃; the reaction time is 1-5h, preferably 2-3 h.
9. The method according to any one of claims 6 to 8, wherein the electrolytic reaction is carried out in a diaphragm-free electrolytic cell, wherein the cathode electrode and the anode electrode of the diaphragm-free electrolytic cell are selected from inert electrodes, preferably one or more of platinum electrode, gold electrode and graphite electrode.
10. The method according to any one of claims 6 to 9, wherein after the electrolysis reaction is finished, the catalyst is separated by an external magnetic field, then washed by dichloromethane and dried for reuse;
filtering the electrolytic reaction solution after recovering the catalyst, washing the solid with water, and drying to obtain beta-carotene;
and (3) circularly applying the filtered filtrate to the next electrolytic reaction, adding sulfuric acid into the filtrate to adjust the pH value to be neutral when applying the filtrate, concentrating to remove the water introduced by the alkali liquor, transferring the filtrate into an electrolytic cell for applying the filtrate, and adding the raw materials to the required amount when applying the filtrate.
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