阅读说明：本技术 一种角黄素异构过滤母液资源化利用的方法 (Method for resource utilization of canthaxanthin isomeric filtration mother liquor ) 是由 宋军伟 张旭 沈宏强 张弈宇 王嘉辉 于 2021-08-25 设计创作，主要内容包括：本发明公开了一种角黄素异构过滤母液资源化利用的方法,包括以含有角黄素过度氧化杂质的异构过滤母液为反应底物,在改性催化剂和还原剂的作用下,经脱氧还原反应制备得到角黄素的步骤。本发明的方法将异构过滤母液中的过度氧化物质在改性催化剂的作用下,脱氧还原为角黄素,有效提升异构反应的总收率,减少了废液产生量。(The invention discloses a method for resource utilization of canthaxanthin isomerization filtering mother liquor, which comprises the step of preparing canthaxanthin by taking the isomerization filtering mother liquor containing excessive oxidation impurities of canthaxanthin as a reaction substrate and carrying out deoxidation reduction reaction under the action of a modified catalyst and a reducing agent. According to the method, the excessive oxidation substances in the isomerized filtered mother liquor are deoxidized and reduced into canthaxanthin under the action of the modified catalyst, so that the total yield of isomerization reaction is effectively improved, and the generation amount of waste liquid is reduced.)

1. A resource utilization method of canthaxanthin isomerization filtering mother liquor is characterized by comprising the step of preparing canthaxanthin by taking the isomerization filtering mother liquor containing excessive oxidation impurities of canthaxanthin as a reaction substrate and carrying out deoxidation reduction reaction under the action of a modified catalyst and a reducing agent.

2. The method as claimed in claim 1, wherein the modified catalyst is prepared by mixing, impregnating and drying rhenium-containing oxide serving as an active component with a promoter and a carrier.

3. The method according to claim 2, wherein the rhenium-containing oxide is selected from at least any one of rhenium dioxide, rhenium heptoxide, rhenium trioxide or rhenium oxide; the cocatalyst is selected from at least any one of manganese oxide, magnesium oxide, antimony trioxide, bismuth trioxide, tin oxide and nickel oxide; the carrier is selected from at least any one of graphene, carbon nano tubes, carbon nano belts, graphitized carbon nitride and molybdenum disulfide.

4. The method according to claim 2 or 3, wherein the impregnation is carried out in a solvent selected from at least any one of methanol, ethanol, water, n-hexane; preferably, the mass ratio of the active component, the cocatalyst, the carrier and the solvent is 1:0.5-4:50-200:500-2000, preferably 1:1-2:80-100: 800-1000.

5. A method according to any of claims 2-4, characterized in that the temperature of the impregnation is 20-60 ℃, preferably 30-40 ℃; the impregnation time is 12-24h, preferably 16-20 h.

6. The method according to any one of claims 2 to 5, wherein the temperature of the drying is 80 to 120 ℃, preferably 90 to 100 ℃; the drying time is 12-24h, preferably 16-20 h.

7. The method according to claim 1, wherein the reducing agent is at least one selected from triphenylphosphine, triphenyl phosphite, sodium sulfite, sodium thiosulfate and sodium sulfide.

8. The method according to claim 1, characterized in that the feeding mass of the modified catalyst is 0.1-2%, preferably 0.5-1% of the isomerization filtration mother liquor; the feeding mass of the reducing agent is 0.1-1% of the isomeric filtration mother liquor, and preferably 0.2-0.5%.

9. The method according to claim 1, wherein the solvent in the isomerization filtration mother liquor is at least any one of ethyl acetate, n-propyl acetate, toluene, n-heptane, methanol, ethanol, isopropanol, tetrahydrofuran and acetone.

10. The method according to claim 1, characterized in that the reaction temperature of the deoxidation reduction reaction is 60-120 ℃, preferably 80-110 ℃; the reaction pressure is 0.1MPaA to 0.6MPaA, preferably 0.1MPaA to 0.3 MPaA; the reaction time is 6-48h, preferably 12-24 h.

Technical Field

The invention belongs to the field of nutritional chemicals, and particularly relates to a method for resource utilization of canthaxanthin isomeric filtration mother liquor.

Background

Canthaxanthin (also known as canthaxanthin) is a carotenoid found in certain mushrooms, crustaceans, fish, algae, eggs, blood and liver. In 1984, the FDA/WHO approved cantharis yellow to be included in food additives and set quality standards. Canthaxanthin can be used as food additive for beverage, ice cream, waffle without adjuvant, flavoring paste, tomato processed product, meat processed product, etc. Cantharis yellow is added into the feed of poultry such as chicken and duck, and the yellow yolk is a yellow orange color which is popular with consumers.

Canthaxanthin can be prepared by a synthetic route such as chemical synthesis or biotechnology, for example, canthaxanthin can be obtained by oxidation of beta-carotene synthesized by Witting reaction. EP1253131a1, CN1417207A, CN110372555A and other patents all report methods for preparing canthaxanthin by using β -carotene as a raw material, and since β -carotene has a structural formula containing a large amount of C ═ C bonds, a large amount of epoxidation byproducts are generated during the oxidation process. In the process reported at present, part of impurities enter the isomeric filtration mother liquor to be directly discarded, which results in low total reaction yield.

Therefore, how to further convert the over-oxidized impurities in the isomerized filtered mother liquor into canthaxanthin so as to improve the total yield of the reaction becomes the key of research.

Disclosure of Invention

In order to solve the problems in the prior art, the invention aims to provide a method for resource utilization of canthaxanthin isomerization filtering mother liquor, which can perform deoxidation and reduction treatment on excessive oxidation impurities in the isomerization filtering mother liquor to obtain canthaxanthin, and improve the total reaction yield.

In order to achieve the above purpose, the technical scheme of the invention is as follows:

a resource utilization method of canthaxanthin isomerization filtering mother liquor comprises the step of taking the isomerization filtering mother liquor containing canthaxanthin over-oxidation impurities as a reaction substrate, and preparing canthaxanthin through deoxidation and reduction reaction under the action of a modified catalyst and a reducing agent.

In a specific embodiment, the modified catalyst is prepared by taking rhenium-containing oxide as an active component, mixing with a promoter and a carrier, impregnating and drying.

In a specific embodiment, the rhenium-containing oxide is selected from at least any one of rhenium dioxide, rhenium heptoxide, rhenium trioxide or rhenium oxide; the cocatalyst is selected from at least any one of manganese oxide, magnesium oxide, antimony trioxide, bismuth trioxide, tin oxide and nickel oxide; the carrier is selected from at least any one of graphene, carbon nano tubes, carbon nano belts, graphitized carbon nitride and molybdenum disulfide.

In a specific embodiment, the impregnation is carried out in a solvent selected from at least any one of methanol, ethanol, water, n-hexane; preferably, the mass ratio of the active component, the cocatalyst, the carrier and the solvent is 1:0.5-4:50-200:500-2000, preferably 1:1-2:80-100: 800-1000.

In a particular embodiment, the temperature of the impregnation is 20 to 60 ℃, preferably 30 to 40 ℃; the impregnation time is 12 to 24 hours, preferably 16 to 20 hours.

In a particular embodiment, the temperature of the drying is between 80 and 120 ℃, preferably between 90 and 100 ℃; the drying time is 12-24h, preferably 16-20 h.

In a specific embodiment, the reducing agent is selected from at least any one of triphenylphosphine, triphenyl phosphite, sodium sulfite, sodium thiosulfate and sodium sulfide.

In a specific embodiment, the feeding mass of the modified catalyst is 0.1-2%, preferably 0.5-1% of the isomerization filtration mother liquor; the feeding mass of the reducing agent is 0.1-1%, preferably 0.2-0.5% of the isomeric filtration mother liquor.

In a specific embodiment, the solvent in the isomerization filtration mother liquor is at least any one of ethyl acetate, n-propyl acetate, toluene, n-heptane, methanol, ethanol, isopropanol, tetrahydrofuran and acetone.

In a specific embodiment, the reaction temperature of the deoxidation reduction reaction is 60-120 ℃, preferably 80-110 ℃; the reaction pressure is 0.1MPaA to 0.6MPaA, preferably 0.1MPaA to 0.3 MPaA; the reaction time is 6-48h, preferably 12-24 h.

Compared with the prior art, the invention adopts the technical scheme, and has the following positive effects:

(1) the method of the invention carries out resource utilization on the waste liquid of the canthaxanthin isomerization filtration mother liquor in the prior art, and obtains the canthaxanthin by carrying out deoxidation and reduction treatment on the excessive oxidation impurities, thereby greatly improving the total yield of the reaction, and finally reaching 98-99 percent of the total yield of the canthaxanthin; without the resource utilization process of the over-oxidized impurities, the canthaxanthin yield is only 82%.

(2) The method can avoid the impurities which are excessively oxidized from being completely treated as solid waste by carrying out resource utilization on the canthaxanthin isomerization filtration mother liquor, thereby reducing the production amount of the waste liquor and the treatment cost of three wastes.

Detailed Description

The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and also includes any other known modifications within the scope of the claims of the present invention.

A method for resource utilization of canthaxanthin isomerization filtering mother liquor comprises the steps of taking the isomerization filtering mother liquor containing canthaxanthin over-oxidation impurities as a reaction substrate, and preparing canthaxanthin through deoxidation reduction reaction under the action of a modified catalyst and a reducing agent.

Wherein the isomerization filtration mother liquor as the reaction substrate is an isomerization filtration mother liquor produced by a canthaxanthin isomerization reaction centrifugal filtration operation, and the isomerization filtration mother liquor generally has a composition of: 65-70% of solvent, 2-5% of canthaxanthin and 25-30% of excessive oxidation impurities of canthaxanthin. The solvent is at least one selected from ethyl acetate, n-propyl acetate, toluene, n-heptane, methanol, ethanol, isopropanol, tetrahydrofuran and acetone, preferably n-propyl acetate, isopropanol and tetrahydrofuran. Specifically, for example, the isomerized mother liquor comprises 67% n-propyl acetate, 4% canthaxanthin, and 29% of a canthaxanthin over-oxidation impurity, wherein the canthaxanthin over-oxidation impurity is, for example, mainly a by-product produced by an epoxidation reaction on a C ═ C double bond.

The deoxidation reduction reaction of the invention reaction temperature is 60-120 ℃, for example including but not limited to 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, preferably 80-110 ℃; the reaction pressure is from 0.1MPaA to 0.6MPaA, including for example but not limited to 0.1MPaA, 0.15MPaA, 0.2MPaA, 0.25MPaA, 0.3MPaA, 0.35MPaA, 0.4MPaA, 0.45MPaA, 0.5MPaA, 0.55MPaA, 0.6MPaA, preferably 0.1MPaA to 0.3 MPaA; the reaction time is 6 to 48h, for example, but not limited to 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h, 44h, 46h, 48h, preferably 12 to 24 h.

Wherein, the feeding mass of the modified catalyst is 0.1-2% of the mass of the isomerization filtration mother liquor, such as but not limited to 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, preferably 0.5-1%; the feeding mass of the reducing agent is 0.1-1% of the mass of the isomerization filtration mother liquor, such as but not limited to 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, and preferably 0.2-0.5%.

The modified catalyst is prepared by taking rhenium oxide as an active component, mixing with a promoter and a carrier, impregnating and drying. Wherein, the oxide of rhenium is selected from at least any one of rhenium dioxide, rhenium heptoxide, rhenium trioxide or rhenium oxide; the cocatalyst is selected from at least one of manganese oxide, magnesium oxide, antimony trioxide, bismuth trioxide, tin oxide and nickel oxide; the carrier is selected from at least any one of graphene, carbon nano tubes, carbon nano belts, graphitized carbon nitride and molybdenum disulfide. The solvent for impregnation is at least one selected from methanol, ethanol, water and n-hexane. Preferably, the mass ratio of the active component, the cocatalyst, the carrier and the solvent is 1:0.5-4:50-200:500-2000, preferably 1:1-2:80-100:800-1000, and more preferably 1:1-1.5:90-95: 850-900.

Wherein, the mixing, dipping and drying processes of the modified catalyst can refer to the prior art and are routine operations in the field. Specifically, the impregnation temperature is controlled to be 20 to 60 ℃ including, for example, but not limited to, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, preferably 30 to 40 ℃; the impregnation time is 12-24h, for example including but not limited to 12h, 14h, 16h, 8h, 20h, 22h, 24h, preferably 16-20 h; the drying temperature is 80-120 deg.C, such as but not limited to 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C, 120 deg.C, preferably 90-100 deg.C; the drying time is 12-24h, for example, including but not limited to 12h, 14h, 16h, 8h, 20h, 22h, 24h, preferably 16-20 h.

The reducing agent is at least one selected from triphenylphosphine, triphenyl phosphite, sodium sulfite, sodium thiosulfate and sodium sulfide, and triphenylphosphine and sodium sulfite are preferable.

After the deoxidation reduction reaction, the conversion rate of 25-30% of canthaxanthin over-oxidation impurities in the canthaxanthin isomerization filtration mother liquor is about 98%, the selectivity of converting the canthaxanthin into the canthaxanthin is higher than 96%, and the resource utilization of the canthaxanthin over-oxidation impurities is effectively realized.

The production process of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

The following examples and comparative examples use the following information on the main raw materials:

the canthaxanthin isomerization reaction filtering mother liquor is prepared by referring to the process of the experimental method (3) in the research on the isomerization of canthaxanthin, Guangdong chemical industry 2017 and 44(10) in the documents of Luo super et al, and the kind of an isomerization solvent is not limited to n-propyl acetate in the method;

n-propyl acetate, toluene, n-heptane, isopropanol, tetrahydrofuran, methanol, ethanol, n-hexane, analytically pure, carbofuran technologies ltd;

triphenylphosphine, triphenyl phosphite, sodium sulfite, sodium thiosulfate, sodium sulfide, rhenium dioxide, rhenium heptoxide, rhenium sesquioxide, rhenium oxide, manganese oxide, magnesium oxide, antimony trioxide, bismuth trioxide, tin oxide, nickel oxide, graphene, carbon nanotubes, carbon nanoribbons, graphitized carbon nitride, molybdenum disulfide, analytically pure, alatin.

The liquid chromatography test conditions of the invention are as follows: 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: 474-476 nm.

According to the result of liquid chromatography, after the content of canthaxanthin isomers is determined based on an external standard method, the content of over-oxidized impurities can be calculated by a subtraction method, so that the reaction conversion rate and the selectivity are finally calculated.

Example 1

Firstly, mixing rhenium heptoxide, manganese oxide, graphene and methanol according to the mass ratio of 1:2:80:800, then soaking at 30 ℃ for 20h, filtering, and drying at 100 ℃ for 16h to obtain the modified catalyst A.

The isomerization reaction filtered mother liquor is taken as a reaction substrate, 1 percent of modified catalyst A and 0.2 percent of triphenylphosphine are added, and the mixture reacts for 24 hours at 80 ℃ and 0.3 MPaA. Reaction substrate composition: 70% n-propyl acetate, 2% canthaxanthin, 28% canthaxanthin over-oxidation impurities. The conversion of the over-oxidized impurities was 98.3% and the selectivity was 96.5%.

Example 2

Firstly, mixing rhenium dioxide, tin oxide, a carbon nano tube and ethanol according to a mass ratio of 1:1:100:1000, then soaking at 40 ℃ for 16h, filtering, and drying at 90 ℃ for 24h to obtain a modified catalyst B.

Using the filtered mother liquor of the isomerization reaction as a reaction substrate, adding 0.1 percent of modified catalyst B and 1 percent of triphenyl phosphite, and reacting for 12 hours at 110 ℃ and 0.1 MPaA. Reaction substrate composition: tetrahydrofuran 65%, canthaxanthin 5%, canthaxanthin 30% over-oxidized impurities. The conversion of the over-oxidized impurities was 97.8% and the selectivity was 96.2%.

Example 3

Firstly, mixing rhenium trioxide, antimony trioxide, graphitized carbon nitride and n-hexane according to the mass ratio of 1:0.5:50:500, then soaking at 60 ℃ for 12 hours, filtering, and drying at 80 ℃ for 20 hours to obtain the modified catalyst C.

Using the filtered mother liquor of isomerization reaction as a reaction substrate, adding 1 percent of modified catalyst C and 0.5 percent of sodium sulfite, and reacting for 48 hours at 60 ℃ under 0.6 MPaA. Reaction substrate composition: 69% toluene, 5% canthaxanthin, 26% canthaxanthin over-oxidation impurities. The conversion of the over-oxidized impurities was 98.7% and the selectivity was 96.7%.

Example 4

Firstly, mixing rhenium dioxide, nickel oxide, molybdenum disulfide and water according to the mass ratio of 1:1.5:90:900, then soaking at 20 ℃ for 24h, filtering, and drying at 120 ℃ for 12h to obtain the modified catalyst D.

Using the filtered mother liquor of the isomerization reaction as a reaction substrate, adding 2 percent of modified catalyst D and 0.1 percent of sodium thiosulfate, and reacting for 6 hours at 120 ℃ and 0.1 MPaA. Reaction substrate composition: 68% n-heptane, 4% canthaxanthin, 28% canthaxanthin over-oxidation impurities. The conversion of the over-oxidized impurities was 98.5% and the selectivity was 96.4%.

Example 5

Firstly, mixing rhenium dioxide, bismuth trioxide, carbon nanobelts and methanol according to the mass ratio of 1:4:95:850, then soaking at 30 ℃ for 20 hours, filtering, and drying at 100 ℃ for 20 hours to obtain the modified catalyst E.

Using the filtered mother liquor of the isomerization reaction as a reaction substrate, adding 1 percent of modified catalyst E and 0.2 percent of sodium sulfide, and reacting for 20 hours at 100 ℃ and 0.2 MPaA. Reaction substrate composition: 66% methanol, 5% canthaxanthin, 29% canthaxanthin over-oxidation impurities. The conversion of the over-oxidized impurities was 98.6% and the selectivity was 96.3%.

Example 6

Firstly, mixing rhenium trioxide, magnesium oxide, graphene and ethanol according to the mass ratio of 1:2:200:2000, then soaking at 40 ℃ for 18h, filtering, and drying at 95 ℃ for 18h to obtain the modified catalyst F.

Using the filtered mother liquor of the isomerization reaction as a reaction substrate, adding 0.8 percent of modified catalyst F and 0.4 percent of triphenyl phosphite, and reacting for 18 hours at 90 ℃ and 0.3 MPaA. Reaction substrate composition: 70% ethanol, 5% canthaxanthin, 25% canthaxanthin over-oxidation impurities. The conversion of the over-oxidized impurities was 98.4% and the selectivity was 96.1%.

Comparative example 1

In the catalyst preparation process, no active component is added, the other preparation processes are the same as those in example 1, the catalyst a is prepared, the reaction conversion rate of the over-oxidized impurities is 38.4%, and the selectivity is 12.1%.

Comparative example 2

In the catalyst preparation process, no promoter component was added, and the other preparation processes were the same as in example 1, to prepare catalyst b, with a conversion of the over-oxidized impurities reaction of 98.4% and a selectivity of 15.2%.

Comparative example 3

No reducing agent is added in the reaction process, other reaction processes are the same as example 1, and the conversion rate of the reaction of the over-oxidized impurities is 0 percent.

While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.