CN114805160A - Method for preparing canthaxanthin by one-step oxidation of beta-carotene - Google Patents
Method for preparing canthaxanthin by one-step oxidation of beta-carotene Download PDFInfo
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- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
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Abstract
The invention discloses a method for preparing canthaxanthin by one-step oxidation of beta-carotene, which comprises the steps of dissolving the beta-carotene in a eutectic solvent, and carrying out oxidation reaction in the presence of a catalyst and ozone to prepare the canthaxanthin. The catalyst is alkaline magnesium salt. The ozone in the invention plays a role of an oxidant, the deep eutectic solvent has an absorption effect on the ozone, and the beta-carotene can be slowly and selectively oxidized to prepare canthaxanthin, so that the carbon-carbon bond breakage is inhibited. The method has the advantages of mild process route conditions, environmental friendliness, recyclable solvent and easiness in industrial production.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for preparing cantharis yellow.
Background
Canthaxanthin is also called canthaxanthin, beta-carotene-4, 4' -dione and Callicarin red. Canthaxanthin has a structure similar to that of beta-carotene except that canthaxanthin has a carbonyl group per cyclohexene ring. The activity of quenching active oxygen and the ability of eliminating free radicals of canthaxanthin are twice of that of beta-carotene and fifty times of that of vitamin E, and the canthaxanthin has wide application in the fields of aquaculture, feed additives, food coloring agents and medicine. The price of canthaxanthin in the international market is more than twice of that of beta-carotene. With the increasing demand of the domestic and foreign markets for cantharis yellow, the synthesis process of cantharis yellow becomes a hot point of research.
At present, the total synthesis method and the beta-carotene oxidation method are industrialized, wherein the direct beta-carotene oxidation method becomes a mainstream process route due to simple process route, mild reaction conditions and high product yield.
US4212827A discloses a method for producing canthaxanthin, which takes chlorate or bromate as an oxidant and iodine as a catalyst to catalyze and oxidize beta-carotene to prepare the canthaxanthin. However, the reaction time of the method is too long, catalyst iodide is difficult to recover, and the treatment of reaction waste liquid is difficult.
CN1277191A continuously introduces iodine halide or iodine elementary substance and metal iodide in an iodine catalytic system to realize co-catalysis, although the method can shorten the reaction time, the iodine halide is toxic and unstable in property.
CN101633633A uses hydrogen peroxide as oxidant and alkali metal chlorate or bromate as catalyst to oxidize beta-carotene to prepare canthaxanthin, the yield of the method can reach 78%, but the waste water still contains a large amount of halogen which is difficult to treat.
CN111825588A takes a metal calcium salt compound as a catalyst, and takes peroxides such as hydrogen peroxide, tert-butyl peroxide and oxygen as oxidants to catalyze and oxidize beta-carotene to prepare canthaxanthin, the method abandons the addition of iodide in the traditional preparation process of canthaxanthin, is more green and environment-friendly, but uses a large amount of solvent in the preparation process, is difficult to recover and is harmful to the bodies of operators.
CN107280065A describes an amino acid type natural eutectic solvent, which comprises three amino acids: the natural eutectic solvent formed by the D/L-proline, the serine and the arginine is low in price, green and environment-friendly, and has double effects of improving physical moisture retention and sensory moisture retention of tobacco. CN106498452A is prepared by taking betaine-urea-water eutectic solvent as electroplating solution, taking pure zinc plate as anode and low carbon steel as cathode, and immersing into the electroplating solution for constant current electroplating. The galvanizing process is safe, non-toxic and environment-friendly. CN110182860A provides a method for preparing nano nickel sulfide based on a eutectic solvent one-step synthesis method, which comprises the steps of mixing any one of amide, carboxylic acid or alcohol with quaternary ammonium salt to obtain a eutectic solvent, introducing the reactant into the eutectic solvent, and reacting to obtain the nano nickel sulfide. The reaction can be carried out at normal temperature and pressure by using the eutectic solvent. The above prior art does not suggest the technical solution of the present invention.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing canthaxanthin by one-step oxidation of beta-carotene, which adopts the beta-carotene with rich productivity and relatively low price as a raw material, improves the selectivity and yield of the canthaxanthin, has simple and safe process, easy recovery of a solvent, no pollution and industrial application value.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing canthaxanthin by one-step oxidation of beta-carotene comprises the following steps: dissolving beta-carotene in eutectic solvent, and carrying out oxidation reaction in the presence of alkaline magnesium salt and ozone to obtain canthaxanthin.
The reaction equation is as follows:
further, the eutectic solvent comprises a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is selected from one or more of positively charged polar amino acids such as lysine, arginine and histidine, and the hydrogen bond donor is selected from one or more of trifluoroacetamide, citric acid and xylitol.
Further, the eutectic solvent further comprises water having a water content of 60 to 90 wt%, preferably 70 to 80 wt%, based on the weight of the eutectic solvent.
The hydrogen bond acceptors such as lysine, arginine and histidine have positive charges, can form short and strong hydrogen bonds with hydrogen bond donors such as trifluoroacetamide, citric acid and xylitol, the action strength of the hydrogen bond acceptors is similar to that of covalent bond protons shared between the donors and the acceptors, the hydrogen bond strength is increased along with the reduction of the distance between the donors and the acceptors, the potential barrier is gradually reduced, and finally, the flat-bottom single-trap potential is generated. At the moment, polar molecule ozone can be adsorbed on the eutectic solvent more stably and released slowly, so that carbon bond breakage is avoided, and selective oxidation of beta-carotene can be realized by matching with an alkaline magnesium salt catalyst.
The stronger the polarity of the hydrogen bond donor is, the higher the strength of the short and strong hydrogen bonds is, the hydrogen bond donor is more easily dissolved in water and a hydrogen bond acceptor to form a eutectic solvent, the better the slow release effect on ozone molecules is, and carbon-carbon bonds are not easy to break.
Preferably, the hydrogen bond acceptor is selected from lysine and the hydrogen bond donor is selected from citric acid.
Further, the mass ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1-4: 1, preferably 1.5 to 2.5: 1.
further, the mass ratio of lysine to citric acid is preferably 1.5-2.5: 1.
the donor and the acceptor can not be matched one by one, and the hydrogen bond acceptor needs to be excessive, so that more effective strong hydrogen bonds are formed.
Further, the basic magnesium salt is one or more of basic magnesium carbonate, magnesium lactate, magnesium chloride, magnesium silicate and magnesium borate whisker, and basic magnesium carbonate is preferred.
Further, the mass ratio of the alkaline magnesium salt to the beta-carotene is 0.05-0.5: 1, preferably 0.1-0.3: 1.
Furthermore, the mass of the eutectic solvent is 10-30 times of that of the beta-carotene.
Further, the oxidation reaction temperature is 0-100 ℃, and preferably 40-80 ℃.
Further, the absolute pressure of the oxidation reaction is 1-5 MPa, preferably 1.5-4 MPa.
Further, the oxidation reaction time is 2-25 h, preferably 5-20 h.
Ozone is a common carbon-carbon bond breaking reaction raw material, if a traditional solvent is used, beta-carotene bonds can be broken, but because ozone is a polar molecule, the absorption capacity of the eutectic solvent to ozone is far greater than that of the traditional solvent, selective oxidation of beta-carotene can be realized by applying the eutectic solvent which is easy to separate, low in steam pressure and high in thermal stability and matching with an alkaline magnesium salt catalyst, the canthaxanthin can be prepared by one-step oxidation, the solvent can be recycled, and compared with the traditional process, the efficient and pollution-free canthaxanthin preparation method is efficient and free.
The cantharis yellow synthesized by the method has the advantages that the reaction conversion rate can reach 98%, the selectivity can reach 98%, and the solvent recovery rate can reach 100%.
The technical scheme of the invention has the beneficial effects that:
1. ozone is used as an oxidant instead of traditional chlorate, bromate or other metal peroxides, so that the method has the advantages of low steam pressure, high thermal stability, avoidance of the problems of high salt content and difficult treatment of wastewater, and realization of recycling of a solvent.
2. Besides magnesium chloride, other alkaline magnesium salt catalysts are insoluble in eutectic solvent and can be easily separated and recycled, and the solvent can be recycled.
3. The eutectic solvent has the advantages of simple preparation, low price, environmental protection, low volatility and strong dissolving capacity, and can absorb ozone molecules, slowly oxidize beta-carotene to generate canthaxanthin, and reduce the yield of carbon-carbon bond breaking byproducts.
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 analysis method used in the specific embodiment of the present invention:
gas chromatograph: agilent7820A, column HP-5(30 m.times.320. mu.m.times.0.25 μm), injection port temperature: 80 ℃; the split ratio is 30: 1; carrier gas flow: 1.5 ml/min; temperature rising procedure: keeping at 40 deg.C for 1min, heating to 80 deg.C at 10 deg.C/min for 0min, heating to 180 deg.C at 5 deg.C/min for 0min, heating to 260 deg.C at 30 deg.C/min for 5 min. Detector temperature: at 260 ℃.
Ozone generators, Kyoho ozone technologies, QJ-8008Y-200A;
beta-carotene, 97.12 wt%, Vanhua Chemicals, Inc.;
dipentene, 99 wt%, Aladdin reagent, Inc.
Example 1
(1) Weighing 300g of lysine and 150g of citric acid, adding 1350g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 3MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 60 ℃, ensuring the pressure of the kettle to be 3Mpa (absolute pressure, the same below), keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and releasing gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 99.75%, cantharis yellow yield: 96.23%, total yield of broken bond by-products: 0.64 percent.
Example 2
(1) Weighing 300g of arginine and 150g of citric acid, adding 1350g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 1.5MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 60 ℃, ensuring the pressure of the kettle to be 1.5MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and releasing gas. Separating catalyst and reaction liquid by filtration, taking organic phase of reaction liquid for detection, beta-HuThe conversion rate of the carotene is as follows: 99.14%, cantharis yellow yield: 95.29%, total yield of broken bond by-products: 0.99 percent.
Example 3
(1) Weighing 300g of histidine and 150g of citric acid, adding 1350g of deionized water to prepare a eutectic solvent, and adding the eutectic solvent into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 4MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 40 ℃, ensuring the pressure of the kettle to be 4MPa, keeping the pressure and the temperature for reaction for 20 hours, cooling the reaction kettle, releasing pressure and discharging gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 98.89%, cantharis yellow yield: 95.24%, total yield of broken bond by-products: 0.80 percent.
Example 4
(1) Weighing 300g of lysine and 150g of trifluoroacetamide, adding 1350g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 3MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 80 ℃, ensuring the pressure of the kettle to be 3MPa, keeping the pressure and the temperature for reaction for 5 hours, cooling the reaction kettle, releasing pressure and discharging gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 98.86%, cantharis yellow yield: 95.00%, total yield of broken bond by-products: 1.02 percent.
Example 5
(1) Weighing 300g of lysine and 150g of xylitol, adding 1350g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 3MPa of O into the autoclave 3 Starting a heater of the high-pressure kettle for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 60 ℃, ensuring the kettle pressure to be 3MPa,keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and releasing gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 98.75%, cantharis yellow yield: 94.90%, total yield of broken bond by-products: 1.01 percent.
Example 6
(1) Weighing 300g of lysine and 150g of citric acid, adding 1350g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of magnesium lactate into the autoclave under the inert gas atmosphere, and filling 3MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 60 ℃, ensuring the pressure of the kettle to be 3MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and discharging gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 99.03%, yield of cantharis yellow: 95.38%, total yield of broken bond by-products: 0.80 percent.
Example 7
(1) Weighing 300g of lysine and 150g of citric acid, adding 1350g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of magnesium chloride into an autoclave in an inert gas atmosphere, and filling 3MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 60 ℃, ensuring the pressure of the kettle to be 3MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and discharging gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 99.11%, cantharis yellow yield: 95.21%, total yield of broken bond by-products: 1.04 percent.
Example 8
(1) Weighing 300g of lysine and 150g of citric acid, adding 1050g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 3MPa of O into the autoclave 3 And starting a heater of the autoclave for stirring, adjusting an air inlet valve and an air outlet valve of the autoclave after the temperature in the autoclave reaches 60 ℃, ensuring the pressure of the autoclave to be 3MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and discharging gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 98.34%, cantharis yellow yield: 94.23%, total yield of broken bond by-products: 1.28 percent.
Example 9
(1) Weighing 300g of lysine and 150g of citric acid, adding 1800g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 3MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 60 ℃, ensuring the pressure of the kettle to be 3MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and discharging gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 98.91, cantharis yellow yield: 94.84%, total yield of broken bond by-products: 1.22 percent.
Example 10
(1) Weighing 300g of lysine and 200g of citric acid, adding 1500g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 3MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 60 ℃, ensuring the pressure of the kettle to be 3MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and discharging gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 98.47%, yield of cantharis yellow: 94.30%, total yield of broken bond by-products: 1.33 percent.
Example 11
(1) Weighing 300g of lysine and 120g of citric acid, adding 1260g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 3MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 60 ℃, ensuring the pressure of the kettle to be 3MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and discharging gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 98.56%, cantharis yellow yield: 94.12%, total yield of broken bond by-products: 1.60 percent.
Example 12
(1) Weighing 300g of lysine and 150g of citric acid, adding 1350g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 9g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 3MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 60 ℃, ensuring the pressure of the kettle to be 3MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and discharging gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 98.02%, cantharis yellow yield: 94.01%, total yield of broken bond by-products: 1.19 percent.
Example 13
(1) Weighing 300g of lysine and 150g of citric acid, adding 1350g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 27g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 3MPa of O into the autoclave 3 And starting a heater of the autoclave for stirring, adjusting an air inlet valve and an air outlet valve of the autoclave after the temperature in the autoclave reaches 60 ℃, ensuring the pressure of the autoclave to be 3MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and discharging gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 99.31%, cantharis yellow yield: 95.64%, total yield of broken bond by-products: 0.81 percent.
Comparative example 1
Under the inert gas atmosphere, 90g of beta-carotene, 18g of basic magnesium carbonate and 1800g of dichloromethane are added into an autoclave, and 1.5MPa of O is charged into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 40 ℃, ensuring the pressure of the kettle to be 1.5MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and releasing gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 35.87%, yield of cantharis yellow: 0%, total yield of broken bond by-products: 34.84 percent.
Comparative example 2
(1) Weighing 300g of alanine and 150g of citric acid, adding 1350g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 1.5MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 40 ℃, ensuring the pressure of the kettle to be 1.5MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and releasing gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 86.94%, yield of cantharis yellow: 13.45%, total yield of broken bond by-products: 70.98 percent.
Comparative example 3
(1) Weighing 300g of glycine and 150g of citric acid, adding 1350g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 1.5MPa of O into the autoclave 3 And starting a heater of the autoclave for stirring, adjusting an air inlet valve and an air outlet valve of the autoclave after the temperature in the autoclave reaches 40 ℃, ensuring the pressure of the autoclave to be 1.5MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and releasing gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 77.098%, yield of cantharis yellow: 32.12%, total yield of broken bond by-products: 42.76 percent.
Comparative example 4
(1) Weighing 300g of glutamic acid and 150g of citric acid, adding 1350g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 1.5MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 40 ℃, ensuring the pressure of the kettle to be 1.5MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and releasing gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 82.675%, yield of cantharis yellow: 36.09%, total yield of broken bond by-products: 44.21 percent.
Comparative example 5
(1) Weighing 300g of lysine and 150g of pentanediol, adding 1350g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 1.5MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 40 ℃, ensuring the pressure of the kettle to be 1.5MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and releasing gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 62%, cantharis yellow yield: 20.22%, total yield of broken bond by-products: 39.99 percent.
Comparative example 6
(1) Weighing 300g of lysine and 150g of citric acid, adding 1350g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene into the autoclave under the inert gas atmosphere, and filling 1.5MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 40 ℃, ensuring the pressure of the kettle to be 1.5MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and releasing gas. Separating the catalyst from the reaction solution by filtration, the reaction solution being obtainedAnd (3) detecting by using an organic phase, wherein the conversion rate of beta-carotene is as follows: 7.34%, cantharis yellow yield: 6.39%, total yield of broken bond by-products: 0.74 percent.
Comparative example 7
(1) Weighing 300g of lysine and 150g of citric acid, adding 500g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 1.5MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 40 ℃, ensuring the pressure of the kettle to be 1.5MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and releasing gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 86.21%, cantharis yellow yield: 45.98%, total yield of broken bond by-products: 37.75 percent.
Comparative example 8
(1) Weighing 300g of lysine and 150g of citric acid, adding 8550g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 1.5MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 40 ℃, ensuring the pressure of the kettle to be 1.5MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and releasing gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 76.13%, yield of cantharis yellow: 33.89%, total yield of broken bond by-products: 40.05 percent.
Comparative example 9
(1) Weighing 300g of lysine and 600g of citric acid, adding 2700g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 1.5MPa of O into the autoclave 3 Starting a heater of the autoclave for stirring, and adjusting an air inlet valve and an air outlet valve of the autoclave after the temperature in the autoclave reaches 40 DEG CAnd ensuring that the kettle pressure is 1.5MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, and releasing pressure to release gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 65.44%, yield of cantharis yellow: 53.28%, total yield of broken bond by-products: 10.28 percent.
Comparative example 10
(1) Weighing 300g of lysine and 60g of citric acid, adding 1080g of deionized water to prepare a eutectic solvent, and adding the eutectic solvent into a high-pressure kettle;
(2) adding 90g of beta-carotene and 18g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 1.5MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 40 ℃, ensuring the pressure of the kettle to be 1.5MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and releasing gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 53.23%, cantharis yellow yield: 41.06%, total yield of broken bond by-products: 10.64 percent.
Comparative example 11
(1) Weighing 300g of lysine and 150g of citric acid, adding 1350g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) adding 90g of beta-carotene and 0.9g of basic magnesium carbonate into an autoclave in an inert gas atmosphere, and filling 1.5MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 40 ℃, ensuring the pressure of the kettle to be 1.5MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and releasing gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 23.11%, cantharis yellow yield: 11.08%, total yield of broken bond by-products: 11.36 percent.
Comparative example 12
(1) Weighing 300g of lysine and 150g of citric acid, adding 1350g of deionized water to prepare a eutectic solvent, and adding into a high-pressure kettle;
(2) under inert gas atmosphere, 90g of beta-carotene was added to the autoclave54g of basic magnesium carbonate, and charging 1.5MPa of O into the autoclave 3 And starting a high-pressure kettle heater for stirring, adjusting an air inlet valve and an air outlet valve of the high-pressure kettle after the temperature in the kettle reaches 40 ℃, ensuring the pressure of the kettle to be 1.5MPa, keeping the pressure and the temperature for reaction for 15 hours, cooling the reaction kettle, releasing pressure and releasing gas. The catalyst and the reaction liquid are separated by filtration, the organic phase of the reaction liquid is taken for detection, and the conversion rate of the beta-carotene is as follows: 80.65%, yield of cantharis yellow: 74.24%, total yield of broken bond by-products: 4.09 percent.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing canthaxanthin by one-step oxidation of beta-carotene comprises the following steps: dissolving beta-carotene in eutectic solvent, and carrying out oxidation reaction in the presence of alkaline magnesium salt and ozone to obtain canthaxanthin.
2. The method according to claim 1, wherein the eutectic solvent comprises a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is selected from one or more of lysine, arginine and histidine, and the hydrogen bond donor is selected from one or more of trifluoroacetamide, citric acid and xylitol.
3. The method according to claim 1 or 2, characterized in that the eutectic solvent further comprises water with a water content of 60-90 wt. -%, preferably 70-80 wt. -%, based on the weight of the eutectic solvent.
4. The method according to any one of claims 1 to 3, wherein: the hydrogen bond acceptor is lysine, and the hydrogen bond donor is citric acid.
5. The method according to any one of claims 1 to 4, wherein: the mass ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1-4: 1, preferably 1.5 to 2.5: 1.
6. the method according to any one of claims 1 to 5, wherein the mass ratio of lysine to citric acid is 1.5 to 2.5: 1.
7. the method according to any one of claims 1 to 6, wherein the basic magnesium salt is one or more of basic magnesium carbonate, magnesium lactate, magnesium chloride, magnesium silicate and magnesium borate whisker, preferably basic magnesium carbonate.
8. The method according to any one of claims 1 to 7, wherein the mass ratio of the basic magnesium salt to the beta-carotene is 0.05 to 0.5:1, preferably 0.1 to 0.3: 1.
9. The method according to any one of claims 1 to 8, wherein the mass of the eutectic solvent is 10 to 30 times that of the β -carotene.
10. The method according to any one of claims 1 to 9, wherein the oxidation reaction temperature is 0 to 100 ℃, preferably 40 to 80 ℃; the absolute pressure of the oxidation reaction is 1-5 MPa, preferably 1.5-4 MPa.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090069417A1 (en) * | 2005-10-11 | 2009-03-12 | Yoav Sharoni | Carotenoid oxidation products as chemopreventive and chemotherapeutic agents |
| US20190054135A1 (en) * | 2016-02-25 | 2019-02-21 | Avivagen Inc. | Plant or microorganism-derived carotenoid-oxygen copolymer compositions, methods of identifying, quantifying and producing same and uses thereof |
| CN109369484A (en) * | 2018-11-22 | 2019-02-22 | 万华化学集团股份有限公司 | A method of canthaxanthin is prepared by beta carotene |
| CN110786534A (en) * | 2019-11-26 | 2020-02-14 | 上海龙殷生物科技有限公司 | Method for improving fragrance of tobacco extract by using carotenoid-producing microorganisms |
| US20210330855A1 (en) * | 2018-07-16 | 2021-10-28 | Systagenix Wound Management, Limited | Nitric oxide producing collagen/orc dressing |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090069417A1 (en) * | 2005-10-11 | 2009-03-12 | Yoav Sharoni | Carotenoid oxidation products as chemopreventive and chemotherapeutic agents |
| US20190054135A1 (en) * | 2016-02-25 | 2019-02-21 | Avivagen Inc. | Plant or microorganism-derived carotenoid-oxygen copolymer compositions, methods of identifying, quantifying and producing same and uses thereof |
| US20210330855A1 (en) * | 2018-07-16 | 2021-10-28 | Systagenix Wound Management, Limited | Nitric oxide producing collagen/orc dressing |
| CN109369484A (en) * | 2018-11-22 | 2019-02-22 | 万华化学集团股份有限公司 | A method of canthaxanthin is prepared by beta carotene |
| CN110786534A (en) * | 2019-11-26 | 2020-02-14 | 上海龙殷生物科技有限公司 | Method for improving fragrance of tobacco extract by using carotenoid-producing microorganisms |
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