阅读说明：本技术 一种β-胡萝卜素氧化制备角黄素的方法 (Method for preparing canthaxanthin by oxidizing beta-carotene ) 是由 沈宏强 张涛 刘英瑞 朱龙龙 李莉 潘亚男 于 2020-07-13 设计创作，主要内容包括：本发明提供了一种β-胡萝卜素氧化制备角黄素的方法,将β-胡萝卜素溶解于溶剂中,在催化剂、氧化剂的共同存在下进行氧化反应,制备得到角黄素；所述催化剂为金属钙盐化合物。本发明以廉价的金属钙盐化合物为催化剂、过氧化物为氧化剂催化氧化反应的进行,具有工艺路线条件温和、环境友好、操作简便、易于工业化生产的优点。(The invention provides a method for preparing canthaxanthin by oxidizing beta-carotene, which comprises the steps of dissolving the beta-carotene in a solvent, and carrying out oxidation reaction in the coexistence of a catalyst and an oxidant to prepare the canthaxanthin; the catalyst is a metal calcium salt compound. The method takes the cheap metal calcium salt compound as the catalyst and the peroxide as the oxidant to catalyze the oxidation reaction, and has the advantages of mild process route conditions, environmental friendliness, simple and convenient operation and easy industrial production.)

1. A method for preparing canthaxanthin by oxidizing beta-carotene is characterized in that the beta-carotene is dissolved in a solvent, and the canthaxanthin is prepared by oxidation reaction under the coexistence of a catalyst and an oxidant; the catalyst is a metal calcium salt compound.

2. The process for the oxidative preparation of canthaxanthin of claim 1, wherein said catalyst is one or more of calcium chloride, calcium bromide, calcium carbonate, calcium phosphate and calcium sulfate, preferably calcium chloride.

3. The method for preparing canthaxanthin by oxidizing beta-carotene according to claim 1 or 2, wherein said oxidizing agent is one or more selected from hydrogen peroxide, t-butyl peroxy-alcohol, m-chloroperoxybenzoic acid and oxygen, preferably t-butyl peroxy-alcohol.

4. The process for the oxidative production of canthaxanthin according to claim 1, wherein the molar ratio of the catalyst to the β -carotene is 0.05 to 0.3, preferably 0.2 to 0.3; the mass ratio of the oxidant to the beta-carotene is 2-20, preferably 10-15.

5. The method for preparing canthaxanthin by oxidizing beta-carotene according to claim 1, wherein said oxidation reaction temperature is 0 to 100 ℃, preferably 40 to 80 ℃.

6. The method for preparing canthaxanthin by oxidizing beta-carotene according to claim 1 or 5, wherein said oxidation reaction time is 2 to 30 hours, preferably 24 to 30 hours.

7. The process for the oxidative preparation of canthaxanthin according to any one of claims 1 to 6, wherein said solvent is an optional organic solvent which does not react with the starting material, preferably one or more of dichloromethane, chloroform, toluene, acetonitrile and acetone.

8. The method for preparing canthaxanthin by oxidizing beta-carotene according to claim 7, wherein the amount of said solvent is 10 to 100 times, preferably 40 to 60 times, the mass of beta-carotene.

9. The method for producing canthaxanthin by oxidation of β -carotene according to claim 1, wherein said oxidation reaction is completed and then quenched, the organic phase is collected by filtration, the solvent is removed, and canthaxanthin is obtained by recrystallization.

10. The method for preparing canthaxanthin by oxidation of β -carotene according to claim 9, wherein the solvent used for recrystallization is one or more selected from acetone, dichloromethane, ethanol, diethyl ether, n-hexane, cyclohexane and n-propyl acetate, preferably acetone.

Technical Field

The invention relates to a method, in particular to a method for preparing canthaxanthin by oxidizing beta-carotene.

Background

Canthaxanthin is one of carotenoids, and natural canthaxanthin is present in crustaceans, fishes, algae, eggs, blood, and liver. In 1950 Roche first synthesized canthaxanthin and added canthaxanthin to chicken feed, and found that the presence of canthaxanthin in egg yolk produced the egg yolk with a reddish orange color that consumers preferred. Canthaxanthin was approved by the FDA (united states food and drug administration) and WHO (world health organization) to be included in food additives and to establish quality standards in 1984. According to pharmacological research in recent years, canthaxanthin has pharmacological effects of resisting oxidation, improving blood lipid change and the like.

At present, there are three main methods for preparing canthaxanthin: natural product extraction, microbial fermentation, chemical synthesis, etc. The natural extraction method is mainly to extract from shrimps and crustaceans, and cannot realize large-scale industrial production due to the limitation of raw materials and extraction cost; the microbial fermentation method also has low strain yield and low extraction content, so that the microbial fermentation method cannot be popularized in a large area at present; the chemical synthesis method has low cost, high content and stable production, thereby being accepted by the market. Among them, the oxidation method of beta-carotene is a one-step oxidation method, and compared with the former two methods, the method has the characteristics of easy operation, simple equipment and the like, so the method is a main method for industrially producing canthaxanthin at present. The early industrial production method is that iodine is used as a catalyst and alkali metal periodate is used as an oxidant; in subsequent research reports, chloric acid, bromic acid and salts thereof are used as oxidants, and selenium oxide or selenic acid and the like are used as catalysts.

As early as in US patent publication US4212827A, Joachim Paust et al reported a process for the catalytic oxidation of beta-carotene using chlorate or bromate as the oxidizing agent and iodine as the catalyst, the reaction equation is as follows:

the method has too long reaction time and needs to use more iodide for initiation. Subsequently, chinese published patent CN1277191A reports the addition of iodine halide, iodine or metal iodide as a co-catalyst on the basis of the above process. The iodine halides used include iodine chloride, iodine trichloride, iodine bromide and iodine tribromide, and the iodine halides may be used in a single species or in a mixture of a plurality of species.

With the continuous and intensive research on oxidation reactions by researchers, a number of oxidation systems have been reported in succession, H₂O₂Oxidizing agents such as sodium sulfite/bromate and sodium hypochlorite are applied to the reaction of preparing canthaxanthin by oxidizing beta-carotene.

The Chinese patent publication CN1793098A uses acid to adjust the pH value of oxidant aqueous solution to 2-5, and oxidizes beta-carotene to prepare canthaxanthin under the condition of 200-800W lamp light irradiation.

Although canthaxanthin can be prepared with moderate yield by the method, iodine, halogenated iodine and other iodine-containing compounds with special toxicity and volatility are needed, due to the characteristic of easy sublimation of iodine, harm is caused to the physical health of operators, special protection measures are inevitably needed to be taken for the operating environment, and the investment of equipment and facilities and potential health hazard to the operators are increased; meanwhile, a large amount of salt-containing wastewater is generated in the reaction process, the discharge amount of three wastes is large, and the environment is not friendly; in industrial production, special protection measures are required to be adopted for operators and operation environments, and the method has the characteristic of inconvenient operation. Therefore, the development of a plurality of novel catalytic oxidation systems for preparing canthaxanthin by the oxidation of beta-carotene has important significance.

Disclosure of Invention

The invention provides a method for preparing canthaxanthin by oxidizing beta-carotene, which takes a cheap metal calcium salt compound as a catalyst and peroxide as an oxidant to catalyze an oxidation reaction and has the advantages of mild process route conditions, environmental friendliness, simple and convenient operation and easy industrial production.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a method for preparing canthaxanthin by oxidizing beta-carotene comprises the steps of dissolving beta-carotene in a solvent, and carrying out oxidation reaction in the coexistence of a catalyst and an oxidant to prepare canthaxanthin; the catalyst is a metal calcium salt compound.

Further, the catalyst is one or more of calcium chloride, calcium bromide, calcium carbonate, calcium phosphate and calcium sulfate, preferably calcium chloride.

Further, the oxidant is one or more of hydrogen peroxide, tert-butyl peroxy alcohol, m-chloroperoxybenzoic acid and oxygen, and tert-butyl peroxy alcohol is preferred.

Further, the molar ratio of the catalyst to the beta-carotene is 0.05-0.3, preferably 0.2-0.3; the mass ratio of the oxidant to the beta-carotene is 2-20, preferably 10-15.

Further, the oxidation reaction temperature is 0-100 ℃, and preferably 40-80 ℃.

Further, the oxidation reaction time is 2-30 h, preferably 24-30 h.

Further, the solvent is an optional organic solvent which does not react with the raw materials, and preferably one or more of dichloromethane, chloroform, toluene, acetonitrile and acetone.

Furthermore, the addition amount of the solvent is 10-100 times, preferably 40-60 times of the mass of the beta-carotene.

Further, the reaction is quenched after the oxidation reaction is completed, the organic phase is collected by filtration, the solvent is removed, and canthaxanthin is obtained by recrystallization.

Further, the solvent used for recrystallization is one or more of acetone, dichloromethane, ethanol, diethyl ether, n-hexane, cyclohexane and n-propyl acetate, and acetone is preferred.

The coordination catalytic oxidation of the beta-carotene is realized by the calcium salt, the addition of iodized salt or elementary iodine in the traditional canthaxanthin preparation process is abandoned, the preparation method is more environment-friendly, the process route conditions are mild, the product yield is high, and the preparation method is more suitable for industrial production.

Detailed Description

The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.

The reagents and solvents used in the examples of the invention were purchased from Aladdin reagent Inc.

Analyzing the content of the product by liquid chromatography and calculating the yield, wherein the conditions of the liquid chromatography are as follows: the on-line measurement was performed by a C30 column (YMC carotenoid S-5um (4.6 × 250mm)) of agilent liquid chromatography, the column temperature: 40 ℃, flow rate: 1.0ml/min, sample size: 10.0. mu.l, detection wavelength: 474nm, eluent: a: acetonitrile, B: and (3) isopropanol.