A preparation of canthaxanthin and a method for its preparation

Abstract

The application provides a canthaxanthin preparation and a preparation method thereof. The preparation method can obtain the canthaxanthin preparation by subjecting beta-carotene to an oxidation reaction under the action of a catalyst, an oxidant and a wall material. The preparation method can effectively reduce the generation rate of by-products in the oxidation process by embedding the canthaxanthin obtained by oxidizing the beta-carotene after adding the wall material in the oxidation process, thereby obviously improving the yield of canthaxanthin in the oxidation product and obviously improving the selectivity of beta-carotene. Meanwhile, since the subsequent post-processing step does not remove the wall material, the obtained canthaxanthin is still embedded in the wall material, thereby effectively improving the storage stability of the canthaxanthin and providing a new method for preparing canthaxanthin.

Description

Technical Field

[0001] This invention belongs to the field of canthaxanthin synthesis technology, specifically relating to a canthaxanthin preparation and its preparation method. Background Technology

[0002] Canthaxanthin, also known as canthaxanthin, β-carotene-4,4'-dione, and canthaxanthin red, has twice the activity of quenching reactive oxygen species and the ability to scavenge free radicals compared to β-carotene, and fifty times that of vitamin E. Therefore, it has wide applications in aquaculture, feed additives, food colorings, and the pharmaceutical industry. Adding canthaxanthin to the feed of poultry such as chickens and ducks can produce a consumer-pleasing orange-yellow color in egg yolks.

[0003] Currently, canthaxanthin can usually be prepared through synthetic routes such as chemical synthesis or biotechnology. CN110372555A discloses a method for preparing canthaxanthin by electrocatalytic oxygen oxidation of β-carotene. The raw material β-carotene is dissolved in an organic solvent, and gaseous oxygen is used as the oxidant. Canthaxanthin is synthesized in one step through electrolytic reaction in an electrocatalytic oxidation device packed with a catalyst. The advantages of this invention are mild reaction conditions, easy control of the reaction process, environmental friendliness, suitability for industrial production, and a canthaxanthin yield exceeding 95%. CN1417207A discloses a method for β-carotene derivatives such as euglenatone and astaxanthin. This method uses an in-situ system and employs hypobromic acid, generated by combining sulfurous acid, hydrogen sulfite, or acidic sulfite with bromate, as the oxidant. Astaxanthin and euglenatone achieved good yields while significantly reducing reaction time. However, since the β-carotene structure contains a large number of C=C bonds, a large number of epoxidation byproducts are generated during the oxidation reaction. The two methods mentioned above cannot effectively inhibit the generation of these byproducts and the preparation methods are relatively complicated, which leads to the need to improve the yield of canthaxanthin.

[0004] Therefore, developing a method for preparing canthaxanthin that can effectively reduce the formation of byproducts during oxidation reactions is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a canthaxanthin preparation and its preparation method. The preparation method involves adding a wall material during the oxidation process to encapsulate the canthaxanthin, effectively reducing the generation of byproducts during oxidation and thereby effectively improving the yield of canthaxanthin and the selectivity of β-carotene in the product, thus providing a new method for the preparation of canthaxanthin.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a method for preparing a canthaxanthin preparation, the method comprising: subjecting β-carotene to an oxidation reaction in the presence of a catalyst, an oxidant and a wall material to obtain the canthaxanthin.

[0008] The preparation method provided by this invention involves oxidizing β-carotene in the presence of a catalyst, an oxidant, and a wall material to obtain canthaxanthin. The method effectively reduces the formation of byproducts during the oxidation process by adding a wall material to encapsulate the oxidized canthaxanthin, thus significantly increasing the yield of canthaxanthin and improving the selectivity of carotene. Furthermore, since the wall material is not removed in subsequent post-processing steps, the final canthaxanthin product remains encapsulated within it, thereby effectively improving the storage stability of canthaxanthin.

[0009] In addition to the above, it was unexpectedly discovered that the preparation method provided by the present invention can effectively reduce the problem of large instantaneous exothermic reaction during oxidation.

[0010] Preferably, the catalyst comprises calcium chloride and / or calcium bromide.

[0011] Preferably, the mass ratio of β-carotene to catalyst is 1:(0.01 to 0.1), for example, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08 or 1:0.09.

[0012] Preferably, the oxidant includes any one or a combination of at least two of potassium chlorate, sodium chlorate, hydrogen peroxide, tert-butanol peroxide, sodium chlorite, or sodium hypochlorite.

[0013] Preferably, the mass ratio of β-carotene to oxidant is 1:(0.2 to 2.5), for example, 1:0.4, 1:0.6, 1:0.8, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2 or 1:2.4, etc.

[0014] Preferably, the wall material comprises any one or a combination of at least two of cyclodextrin compounds, lignin sulfonates, gelatin, starch, or gum arabic.

[0015] Preferably, the mass ratio of β-carotene to wall material is 1:(2-20), for example, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16 or 1:18.

[0016] As a preferred technical solution of the present invention, limiting the mass ratio of β-carotene to wall material can optimize the performance of the final canthaxanthin product. On the one hand, if the amount of wall material added is too low, the canthaxanthin cannot be effectively encapsulated, which will lead to a decrease in the yield of canthaxanthin in the final product and a decrease in storage stability. On the other hand, if the amount of wall material added is too high, the canthaxanthin product will be affected by the excessive content of wall material, thus affecting the normal use of canthaxanthin.

[0017] Preferably, the reaction temperature at which the oxidation reaction occurs is 15–60°C, such as 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, or 55°C, and more preferably 30–50°C.

[0018] Preferably, the reaction time for the oxidation reaction is 4 to 24 hours, such as 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours or 22 hours, and more preferably 6 to 20 hours.

[0019] Preferably, the specific method for the oxidation reaction includes the following steps:

[0020] (1) Dissolve the oxidant, catalyst and wall material in water to obtain a mixed solution; dissolve β-carotene in an organic solvent to obtain a β-carotene organic solution;

[0021] (2) Mix the mixture solution obtained in step (1) with the β-carotene organic solution to complete the oxidation reaction.

[0022] Preferably, the mass ratio of β-carotene to organic solvent in step (1) is 1:(10-80), for example, 1:20, 1:30, 1:40, 1:50, 1:60 or 1:70.

[0023] Preferably, the organic solvent in step (1) includes any one or a combination of at least two of chloroform, dichloromethane, dichloroethane, ethanol, acetone or ethyl acetate.

[0024] Preferably, the dissolution temperature of the oxidant, catalyst and wall material in water in step (1) is 30 to 70°C, such as 35°C, 40°C, 45°C, 50°C, 55°C, 60°C or 65°C.

[0025] Preferably, the mass ratio of wall material to water in step (1) is 1:(0.25~20), for example 1:0.5, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16 or 1:18, etc.

[0026] Preferably, the oxidation reaction further includes solvent removal and spray drying steps after completion.

[0027] As a preferred embodiment of the present invention, the preparation method includes the following steps:

[0028] (1) Dissolve the oxidant, catalyst and wall material in water at 30-70℃ to obtain a mixed solution; dissolve β-carotene in an organic solvent to obtain a β-carotene organic solution;

[0029] (2) The mixture solution obtained in step (1) is mixed with the β-carotene organic solution to allow the β-carotene to undergo an oxidation reaction at 15-60°C for 4-24 hours. The solvent is removed and the mixture is spray-dried to obtain the canthaxanthin preparation.

[0030] In a second aspect, the present invention provides a canthaxanthin preparation, which is prepared by the preparation method described in the first aspect.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] (1) The preparation method provided by the present invention obtains the canthaxanthin preparation by oxidizing β-carotene under the combined action of a catalyst, an oxidant, and a wall material. The preparation method effectively reduces the generation of by-products during the oxidation process by adding a wall material during the oxidation process, thereby significantly improving the yield of canthaxanthin in the product and also effectively improving the selectivity of carotene. At the same time, since the subsequent post-processing steps do not remove the wall material in the canthaxanthin preparation, the storage stability of canthaxanthin is effectively improved. Specifically, the product obtained by the preparation method provided by the present invention has a canthaxanthin yield as high as 83-91%, a peroxide yield as low as 2.4-8%, a purity of 99.2-99.7% before storage, a purity of 98.5-99.5% after 30 days of storage, and a purity decrease rate of only 0.2-0.7%.

[0033] (2) The preparation method provided by the present invention can also effectively reduce the problem of large instantaneous exothermic reaction in oxidation reaction. Detailed Implementation

[0034] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0035] Example 1

[0036] A method for preparing a canthaxanthin preparation, the method comprising the following steps:

[0037] (1) Potassium chlorate, calcium chloride, lignin sulfonate (borregaard, CY-NA) and water in a mass ratio of 1:0.5:10:10 are mixed at 35°C to obtain a mixture solution. β-carotene (Zhejiang Medicine, food grade) and chloroform in a mass ratio of 1:50 are mixed to obtain a β-carotene organic solution.

[0038] (2) The mixture solution obtained in step (1) is mixed with the β-carotene organic solution (the mass ratio of β-carotene to lignin sulfonate is 1:10) so that β-carotene undergoes an oxidation reaction at 35°C for 24 hours. After desolventizing and spray drying, the canthaxanthin preparation is obtained.

[0039] Example 2

[0040] A method for preparing a canthaxanthin preparation, the method comprising the following steps:

[0041] (1) Hydrogen peroxide, calcium bromide, gelatin (Rosselot) and water in a mass ratio of 0.2:0.01:2:0.5 were mixed at 40°C to obtain a mixture solution. β-carotene (Zhejiang Medicine, food grade) and dichloromethane in a mass ratio of 1:10 were mixed to obtain a β-carotene organic solution.

[0042] (2) The mixture solution obtained in step (1) is mixed with the β-carotene organic solution (the mass ratio of β-carotene to gelatin is 1:2) so that β-carotene undergoes an oxidation reaction at 50°C for 15 h. After desolventizing and spray drying, the canthaxanthin preparation is obtained.

[0043] Example 3

[0044] A method for preparing a canthaxanthin preparation, the method comprising the following steps:

[0045] (1) Peroxide tert-butanol, calcium bromide, starch (Zhucheng Xingmao) and water in a mass ratio of 2.5:0.1:20:400 were mixed at 40°C to obtain a mixture solution. β-carotene (Zhejiang Medicine, food grade) and dichloroethane in a mass ratio of 1:80 were mixed to obtain a β-carotene organic solution.

[0046] (2) The mixture solution obtained in step (1) is mixed with the β-carotene organic solution (the mass ratio of β-carotene to starch is 1:20) so that the β-carotene undergoes an oxidation reaction at 60°C for 5 hours. After desolventizing and spray drying, the canthaxanthin preparation is obtained.

[0047] Example 4

[0048] A method for preparing a canthaxanthin preparation, which differs from Example 1 only in that the mass ratio of β-carotene to wall material is 1:2, while the other raw materials, parameters and preparation methods are the same as in Example 1.

[0049] Example 5

[0050] A method for preparing a canthaxanthin preparation differs from Example 1 only in that the mass ratio of β-carotene to wall material is 1:20, while the other raw materials, parameters, and preparation methods are the same as in Example 1.

[0051] Example 6

[0052] A method for preparing a canthaxanthin preparation differs from Example 1 only in that the mass ratio of β-carotene to wall material is 1:1.5, while the other raw materials, parameters, and preparation methods are the same as in Example 1.

[0053] Comparative Example 1

[0054] A method for preparing a canthaxanthin preparation, which differs from Example 1 only in that lignin sulfonate is not added, while other raw materials, parameters and preparation methods are the same as in Example 1.

[0055] Comparative Example 2

[0056] A method for preparing a canthaxanthin preparation, which differs from Example 2 only in that gelatin is not added, while the other raw materials, parameters and preparation methods are the same as in Example 2.

[0057] Comparative Example 3

[0058] A method for preparing a canthaxanthin preparation, which differs from Example 3 only in that starch is not added, while other raw materials, parameters and preparation methods are the same as in Example 1.

[0059] Performance testing:

[0060] (1) Yield: The content of the product was analyzed by liquid chromatography and the yield was calculated. The parameters of the liquid chromatography used are as follows:

[0061] Chromatographic column: Agilent WAX (30m×0.32mm×0.25mm); Injector temperature: 230℃; Split ratio: 30:1; Column flow rate: 1.5mL / min; Column temperature: starting from 180℃, increasing to 230℃ at 5℃ / min, and holding for 15min; Detector temperature: 280℃; H2 flow rate: 35mL / min; Air flow rate: 350mL / min.

[0062] (2) Storage stability: The product was stored in a nitrogen atmosphere for 30 days, and the change in purity before and after storage was analyzed by liquid chromatography.

[0063] The products obtained in Examples 1-6 and Comparative Examples 1-3 were tested according to the above test methods, and the test results are shown in Table 1:

[0064] Table 1

[0065]

[0066] As can be seen from the data in Table 1, the yield of the oxidation reaction is significantly improved after adding the wall material using the preparation method provided by this invention. This is because the encapsulation of the wall material blocks excessive oxidation, thereby reducing the generation of excessive oxidation impurities. At the same time, the wall material in the obtained canthaxanthin preparation can also effectively isolate the effects of air and light on canthaxanthin, thereby improving the storage stability of canthaxanthin.

[0067] Specifically, the yields of canthaxanthin in Examples 1-6 were as high as 83-91%, the yields of peroxides were as low as 2.4-8%, the purity before storage was 99.2-99.7%, the purity after 30 days of storage was 98.5-99.5%, and the purity decrease rate was only 0.2-0.7%.

[0068] Comparing the data of Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, and Example 3 and Comparative Example 3, it can be seen that the yield of canthaxanthin in the product obtained without the addition of wall material is significantly reduced, the yield of peroxide is significantly increased, and the purity decrease rate before and after storage is as high as 4.1-5.7%, indicating poor storage stability.

[0069] The applicant declares that this invention illustrates a canthaxanthin preparation and its preparation method through the above embodiments, but this invention is not limited to the above embodiments, that is, it does not mean that this invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of the raw materials of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. A method for preparing a canthaxanthin preparation, characterized in that, The preparation method includes: oxidizing β-carotene under the action of a catalyst, an oxidant, and a wall material to obtain the canthaxanthin preparation; The preparation method includes the following steps: (1) Dissolve the oxidant, catalyst and wall material in water at 30~70℃ to obtain a mixed solution; dissolve β-carotene in an organic solvent to obtain a β-carotene organic solution; the oxidant includes any one or a combination of at least two of potassium chlorate, sodium chlorate, hydrogen peroxide, peroxytert-butanol, sodium chlorite or sodium hypochlorite; the catalyst includes calcium chloride and / or calcium bromide; the wall material includes any one or a combination of at least two of cyclodextrin compounds, lignin sulfonate, gelatin, starch or gum arabic; (2) The mixture solution obtained in step (1) is mixed with the β-carotene organic solution to allow the β-carotene to undergo an oxidation reaction at 15~60℃ for 4~24 h, followed by desolventizing and spray drying to obtain the canthaxanthin preparation; The mass ratio of β-carotene to wall material is 1:(2~20).

2. The preparation method according to claim 1, characterized in that, The mass ratio of β-carotene to catalyst is 1:(0.01~0.1).

3. The preparation method according to claim 1, characterized in that, The mass ratio of β-carotene to oxidant is 1:(0.2~2.5).

4. The preparation method according to claim 1, characterized in that, The oxidation reaction occurs at a temperature of 30~50℃.

5. The preparation method according to claim 1, characterized in that, The oxidation reaction takes 6 to 20 hours.

6. The preparation method according to claim 1, characterized in that, The mass ratio of β-carotene to organic solvent in step (1) is 1:(10~80).

7. The preparation method according to claim 1, characterized in that, The organic solvent in step (1) includes any one or at least two of chloroform, dichloromethane, dichloroethane, ethanol, acetone or ethyl acetate.

8. The preparation method according to claim 1, characterized in that, The mass ratio of wall material to water in step (1) is 1:(0.25~20).

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