A capsanthin, its preparation method and application

Abstract

The present invention relates to the technical field of pigment separation and extraction, and specifically discloses a capsanthin, a preparation method thereof and an application thereof. The method of the present invention includes: (1) saponifying a capsanthin raw material to obtain a saponified solution; the saponification is carried out in the presence of an alcohol, water, an alkali and sodium gluconate; the alcohol is propylene glycol; (2) after adjusting the pH value of the saponified solution, first mixing it with silica having a particle size of 200 - 300 μm, and then mixing it with silica having a particle size of 50 - 100 μm to obtain a mixed material; the mass ratio of the silica having a particle size of 200 - 300 μm to the silica having a particle size of 50 - 100 μm is (10 - 13):1; (3) using a subcritical method to extract the mixed material. The present invention has an ideal yield, is suitable for industrial production, and can obtain a capsanthin product with a high content of trans-capsanthin and in powder form.

Description

Technical Field

[0001] The present invention relates to the technical field of pigment separation and extraction, and specifically, to a capsanthin in powder form with a high content of trans-capsanthin, its preparation method and application. Background Art

[0002] Capsanthin is a kind of fat-soluble, orange-red tetraterpenoid compound containing multiple components extracted from chili peppers, which is healthy, safe and has good coloring ability. Among capsanthin, 70% - 80% of the pigments exist in the form of ester compounds (monoester or diester). It mainly includes: the red series with relatively large polarity, capsanthin and capsorubin; the yellow series with relatively small polarity, β-carotene, β-cryptoxanthin, zeaxanthin, and other pigment components with relatively small contents.

[0003] As an edible pigment with certain health care effects, it has effects such as anti-tumor, anti-inflammatory, preventing diabetes, reducing blood lipid, and enhancing immunity. It is one of the natural class A pigments that are allowed to be used infinitely and is applied in aspects such as food coloring and feed addition, having broad market application prospects.

[0004] With the development of the market, the application of capsanthin in feed has gradually increased. Animals cannot synthesize carotenoids, but can absorb carotenoids from natural-source feed and deposit them in different tissues such as egg yolks, skin, and fat to color them. The higher the proportion of trans-capsanthin, the more the red value increases in the color difference detection of the feeding effect. That is, the higher the proportion of trans-capsanthin in the total carotenoids, the better the coloring effect. Under the condition of ensuring the same coloring effect, the addition amount of capsanthin can be reduced.

[0005] Currently, the existing separation and purification of capsanthin mostly adopt solvent separation, silica gel separation or resin separation, which are not suitable for large-scale industrial production. In addition, capsanthin has thermal instability, and there is pigment thermal loss during the solvent removal process. Therefore, it is necessary to improve the research on the separation method of pigments in capsanthin. Summary of the Invention

[0006] One of the purposes of the present invention is to provide a method for simply separating and preparing a powdered capsanthin containing high trans-capsanthin from capsanthin.

[0007] To achieve this purpose, the technical solution of the present invention is as follows:

[0008] A method for preparing capsanthin, which includes:

[0009] (1) Saponifying the capsanthin raw material to obtain a saponified solution; the saponification is carried out in the presence of alcohol, water, alkali and sodium gluconate; the alcohol is propylene glycol;

[0010] (2) After adjusting the pH value of the saponification solution, first mix it with silicon dioxide having a particle size of 200 - 300 μm, and then mix it with silicon dioxide having a particle size of 50 - 100 μm to obtain a mixed material; the mass ratio of the silicon dioxide having a particle size of 200 - 300 μm to the silicon dioxide having a particle size of 50 - 100 μm is (10 - 13):1;

[0011] (3) Use the subcritical method to extract the mixed material.

[0012] In the present invention, the capsanthin raw material is a conventional commercially available capsanthin product in the art. The particle size is D 90 data. The alkali is KOH and / or NaOH.

[0013] The present invention uses ordinary conventional capsanthin as the raw material and first conducts a saponification reaction. It is particularly found during the research that if sodium gluconate is specifically added during saponification, the dispersibility and fluidity of the saponification solution can be improved, so that the saponification reaction proceeds more fully within the same reaction time, and it is beneficial to increase the content of trans-capsanthin in the final product.

[0014] In addition, the present invention also innovatively separates the saponified saponification solution in a subcritical manner. By combining different particle sizes with a specific mixing method, specific solid auxiliary material silicon dioxide is mixed with the saponification solution as the extraction object. The texture of the mixed material is loose and uniform. After the pigment component is combined with silicon dioxide for extraction, the retention of the color value can be better realized, and the proportion of trans-capsanthin in the product can be increased.

[0015] Specifically, the present invention mixes and cooperates two specific particle sizes of silicon dioxide in sequence, ensuring that when the material mixed with the saponification solution is subjected to subsequent subcritical extraction, the pigment component therein is neither prone to agglomeration nor isolated from the solvent by being wrapped by silicon dioxide, improving the extraction effect and ensuring the proportion of trans-capsanthin in the product.

[0016] The present invention specifically adjusts the pigment properties during the saponification reaction through a specific method, combines with a specific mixing method of a specific solid auxiliary material, and combines with a subcritical extraction method, which can quickly separate the red and yellow pigments at a lower temperature, remove the yellow pigment in the raw material (the hue of the extract ≤ 0.94), effectively reduce pigment loss, and this method does not use solvents such as hexane and acetone, avoiding the residue of harmful solvents.

[0017] Moreover, in the saponification stage of the present invention, propylene glycol is particularly used, which can not only effectively disperse the raw materials and improve the reaction effect, but also avoid being soluble in the subcritical extractant, reducing the treatment pressure for the recycling of the subcritical extractant. And if propylene glycol is not added, during the saponification process, the saponification liquid is likely to form lumps and the reaction cannot proceed. A large amount of alkaline water needs to be added to maintain the saponification liquid as a uniform paste to keep the reaction going. At this time, a large loss in color value and an increase in the amount of silica used will occur subsequently.

[0018] In the method of the present invention, the mass ratio of the capsanthin raw material, water and sodium gluconate is 1:(0.1 - 0.15):(0.001 - 0.0015), preferably 1:(0.125 - 0.15):(0.001 - 0.00125).

[0019] The mass ratio of the capsanthin raw material to the alkali is 1:(0.15 - 0.25), preferably 1:(0.2 - 0.22); the mass ratio of the capsanthin raw material to propylene glycol is 1:(0.3 - 0.35), preferably 1:(0.3 - 0.325).

[0020] The addition of an excessive amount of alkali can ensure the full progress of the saponification reaction. At this time, generally, an excessive amount of alkali needs to be added in cooperation, and at the same time, a certain amount of water is added to ensure the realization of the reaction.

[0021] In step (1) of the method of the present invention, the reaction temperature of the saponification is 60 - 70 °C and the time is 1 - 4 h; first, the capsanthin raw material is mixed with propylene glycol, and then mixed with water, alkali and sodium gluconate;

[0022] In step (2), the pH value of the saponification liquid is adjusted to 7 - 9.

[0023] During the saponification reaction of the present invention, through the proper combination of temperature and time, the saponification effect, production efficiency and the retention rate of the product pigment can be taken into account. First, mixing the raw materials with propylene glycol is more conducive to the full dispersion of the raw materials and improves the reaction uniformity.

[0024] In the method of the present invention, the mass ratio of the saponification liquid after adjusting the pH value to the total silica is 1:(2 - 5), preferably 1:(2.4 - 2.5). The total silica includes silica with a particle size of 200 - 300 μm and silica with a particle size of 50 - 100 μm.

[0025] The addition of a specific proportion of silica can not only make the saponification liquid into a loose and uniform material, which is conducive to the subsequent subcritical extraction, but also ensure the pigment content of the final product (when the amount of silica added is large, the proportion of the pigment content in the final product decreases).

[0026] In step (3) of the method of the present invention, the subcritical extraction solvent is butane, the extraction temperature is 40 - 50 °C, the material - liquid ratio is 1:(3 - 5), the pressure is 0.5 - 1.5 Mpa, the extraction time is 1 - 1.5 h, the number of extraction times is 2 - 5 times, and after extraction, butane is evaporated at 55 - 60 °C.

[0027] The combination of each subcritical condition of the present invention can achieve an ideal extraction effect. Moreover, the present invention especially studies the number of extraction times and particularly finds that in the extraction system of the present invention, it is not that the more extraction times, the better. When the number of extraction times is increased, it will help to increase the proportion of trans - capsanthin, but at the same time, the yield of the product will be lost. Therefore, in order to balance the proportion of trans - capsanthin and the product yield, the number of extraction times is preferably 2 - 5 times.

[0028] The present invention also provides a capsanthin product, which is prepared by the above - mentioned method.

[0029] In the capsanthin product of the present invention, trans - capsanthin accounts for 45 - 60% of the total carotenoids.

[0030] The above - mentioned method of the present invention can obtain a capsanthin with a hue ≤ 0.94 while obtaining a product with a high proportion of trans - capsanthin.

[0031] The present invention further provides the application of the above - mentioned capsanthin product in the preparation of feed and a feed additive comprising the above - mentioned capsanthin product.

[0032] It has been recorded in the prior art that capsanthin can be used as a feed additive to produce a coloring effect on animal tissues such as eggs (for example: Research on the effects of two natural pigments on the egg quality of wheat - soybean meal - based diets; Research on the regulation of egg yolk color in wheat - based diets by red pepper extracts). By using the feed additive of the present invention, good red coloring effects can be obtained on tissues such as egg yolks and skins with a small - dose addition.

[0033] The beneficial effects of the present invention are at least as follows:

[0034] In the process of separating and purifying capsanthin of the present invention, harmful solvents such as n - hexane and acetone are not used, there is no pigment loss caused by solvent removal. In addition, the operation is simple, the yield is ideal, it is suitable for industrial production, and a capsanthin product with a high content of trans - capsanthin (45 - 60%) in powder form can be obtained. Detailed Embodiments

[0035] The following will describe in detail the preferred embodiments of the present invention in conjunction with the examples. It should be understood that the following examples are given only for the purpose of illustration and are not used to limit the scope of the present invention. Those skilled in the art can make various modifications and substitutions to the present invention without departing from the purpose and spirit of the present invention.

[0036] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods. Unless otherwise specified, the materials, reagents, etc. used in the following examples can all be obtained commercially or prepared by conventional methods in this field.

[0037] In the present invention, for the detection methods of trans - capsanthin and total carotenoid content, refer to: DB13 / T 5159 - 2019; for the detection method of color value, refer to: GB 1886.34 - 2015; for the detection method of hue, refer to: GB 1886.34 - 2015.

[0038] Example 1

[0039] This example provides a method for preparing high - trans powdered capsanthin, and the steps are as follows:

[0040] (1) Take 40 kg of capsanthin (purchased from Capsanthin E300 of Chenguang Biotech Group), add 12 kg of propylene glycol, and stir to obtain a first mixture.

[0041] (2) Dissolve 8.8 kg of potassium hydroxide and 0.04 kg of sodium gluconate in 6 kg of water, add it to the above - mentioned first mixture, saponify at 66 °C for 2 h to obtain a saponified solution; add hydrochloric acid to adjust the pH to 9; add 150 kg of silicon dioxide with a particle size D 90 of 250 μm and stir, then add 15 kg of silicon dioxide with a particle size D 90 of 60 μm, stir evenly to obtain a second mixture.

[0042] (3) Put the above - mentioned second mixture into a sub - critical device, add butane according to a liquid - to - solid ratio of 1:3, extract 3 times at 0.6 MPa and 40 °C for 1 h each time, and evaporate at 55 °C to obtain an extract - 3.05 kg of capsanthin yellow. The residue is powdered capsanthin.

[0043] After calculation in the above method: for the extract, the color value is 701 and the hue is 0.865; in the residue, the proportion of trans - capsanthin in total carotenoid is 45.28%.

[0044] Example 2

[0045] This example provides a method for preparing high - trans powdered capsanthin, and the steps are as follows:

[0046] (1) Take 40 kg of capsanthin (purchased from Capsanthin E300 of Chenguang Biotech Group), add 13 kg of propylene glycol, and stir to obtain a first mixture.

[0047] (2) Dissolve 8.5 kg of potassium hydroxide and 0.05 kg of sodium gluconate in 5 kg of water, add it to the above first mixture, saponify at 65 °C for 2 h to obtain a saponified solution; add hydrochloric acid to adjust the pH to 7.5; add 150 kg of silicon dioxide with a particle size D 90 of 290 μm and stir, then add 12 kg of silicon dioxide with a particle size D 90 of 85 μm, stir evenly to obtain a second mixture.

[0048] (3) Put the above second mixture into a subcritical device, add butane according to a liquid-to-material ratio of 1:5, extract 5 times at 1.4 MPa and 48 °C for 1.2 h each time, and evaporate at 57 °C to obtain 6.48 kg of the extract - capsanthin. The residue is powdered capsorubin.

[0049] Calculated in the above method: for the extract, the color value is 693 and the hue is 0.936; the proportion of trans-capsorubin in the residue accounts for 59.64% of the total carotenoids.

[0050] Comparative Example 1

[0051] This comparative example provides a method for preparing capsorubin, and the steps are as follows:

[0052] (1) Take 40 kg of capsorubin (purchased from Chili Red E300 of Chenguang Biotech Group), add 12 kg of propylene glycol, and stir to obtain a first mixture.

[0053] (2) Dissolve 8.8 kg of potassium hydroxide in 6 kg of water, add it to the above first mixture, saponify at 66 °C for 2 h to obtain a saponified solution; add hydrochloric acid to adjust the pH to 9; add 150 kg of silicon dioxide with a particle size D 90 of 250 μm and stir, then add 15 kg of silicon dioxide with a particle size D 90 of 60 μm, stir evenly to obtain a second mixture.

[0054] (3) Put the above second mixture into a subcritical device, add butane according to a liquid-to-material ratio of 1:3, extract 3 times at 0.6 MPa and 40 °C for 1 h each time, and evaporate at 55 °C to obtain 3.44 kg of the extract - capsanthin. The residue is powdered capsorubin.

[0055] Calculated in the above method: for the extract, the color value is 706 and the hue is 0.921; the proportion of trans-capsorubin in the residue accounts for 43.59% of the total carotenoids.

[0056] Comparative Example 2

[0057] This comparative example provides a method for preparing powdered capsanthin, which is generally the same as the method in Example 1, except that the sodium gluconate in step (1) is replaced with the same amount of HT-HPC type polycarboxylate superplasticizer (purchased from Shanxi Huangteng Chemical Co., Ltd.). The extract is 2.73 kg of capsanthin.

[0058] Finally, the extract has a color value of 652 and a hue of 0.923; the proportion of trans-capsanthin in the raffinate accounts for 41.85% of the total carotenoids.

[0059] Comparative Example 3

[0060] This comparative example provides a method for preparing powdered capsanthin, which is generally the same as the method in Example 1, except that in step (2), silica is replaced with starch having the same amount and particle size combination, and the extract is 3.10 kg of capsanthin.

[0061] Finally, the extract has a color value of 574 and a hue of 0.877; the proportion of trans-capsanthin in the raffinate accounts for 44.79% of the total carotenoids.

[0062] Comparative Example 4

[0063] This comparative example provides a method for preparing powdered capsanthin, which is generally the same as the method in Example 1, except that in step (2), after adjusting the pH of the saponified solution, 145 kg of silica with a particle size D 90 of 250 μm is added, and then 20 kg of silica with a particle size D 90 of 60 μm is added, and the extract is 2.97 kg of capsanthin.

[0064] Finally, the extract has a color value of 549 and a hue of 0.882; the proportion of trans-capsanthin in the raffinate accounts for 43.61% of the total carotenoids.

[0065] Comparative Example 5

[0066] This comparative example provides a method for preparing powdered capsanthin, which is generally the same as the method in Example 1, except that in step (2), after adjusting the pH of the saponified solution, 150 kg of silica with a particle size D 90 of 400 μm is added, and then 15 kg of silica with a particle size D 90 of 20 μm is added, and the extract is 2.82 kg of capsanthin.

[0067] Finally, the extract has a color value of 596 and a hue of 0.868; the proportion of trans-capsanthin in the raffinate accounts for 42.57% of the total carotenoids.

[0068] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made thereto based on the present invention, which are obvious to those skilled in the art. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of the present invention claimed.

Claims

1. A method for preparing capsanthin, characterized in that, Comprising: (1) Saponifying the capsanthin raw material to obtain a saponified solution; the saponification is carried out in the presence of alcohol, water, alkali and sodium gluconate; the alcohol is propylene glycol; (2) After adjusting the pH value of the saponified solution, first mixing it with silica with a particle size of 200 - 300 μm, and then mixing it with silica with a particle size of 50 - 100 μm to obtain a mixed material; the mass ratio of silica with a particle size of 200 - 300 μm to silica with a particle size of 50 - 100 μm is (10 - 13):1; (3) Using the subcritical method to extract the mixed material.

2. The method according to claim 1, characterized in that, The mass ratio of the capsanthin raw material, water and sodium gluconate is 1:(0.1 - 0.15):(0.001 - 0.0015).

3. The method according to claim 1 or 2, characterized in that, The mass ratio of the capsanthin raw material to the alkali is 1:(0.15 - 0.25), and the mass ratio of the capsanthin raw material to propylene glycol is 1:(0.3 - 0.35).

4. The method according to claim 1 or 2, characterized in that, In step (1), the reaction temperature of the saponification is 60 - 70 °C, and the time is 1 - 4 h; first mix the capsanthin raw material with propylene glycol, and then mix it with water, alkali and sodium gluconate; In step (2), the pH value of the saponified solution is adjusted to 7 - 9.

5. The method according to claim 3, characterized in that In step (1), the reaction temperature of the saponification is 60 - 70 °C, and the time is 1 - 4 h; first mix the capsanthin raw material with propylene glycol, and then mix it with water, alkali and sodium gluconate; In step (2), the pH value of the saponified solution is adjusted to 7 - 9.

6. The method according to any one of claims 1, 2, and 5, characterized in that The mass ratio of the saponified solution after adjusting the pH value to the total silica is 1:(2 - 5), and the total silica includes silica with a particle size of 200 - 300 μm and silica with a particle size of 50 - 100 μm.

7. The method according to claim 3, wherein The mass ratio of the saponified solution after adjusting the pH value to the total silica is 1:(2 - 5), and the total silica includes silica with a particle size of 200 - 300 μm and silica with a particle size of 50 - 100 μm.

8. The method according to claim 4, wherein The mass ratio of the saponified solution after adjusting the pH value to the total silica is 1:(2 - 5), and the total silica includes silica with a particle size of 200 - 300 μm and silica with a particle size of 50 - 100 μm.

9. The method according to any one of claims 1, 2, 5, 7, and 8, characterized in that, In step (3), the subcritical extraction solvent is butane, the extraction temperature is 40 - 50 °C, the solid - liquid ratio is 1:(3 - 5), the pressure is 0.5 - 1.5 Mpa, the extraction time is 1 - 1.5 h, the extraction times are 2 - 5 times, and butane is evaporated at 55 - 60 °C after extraction.

10. The method according to claim 3, wherein In step (3), the subcritical extraction solvent is butane, the extraction temperature is 40 - 50 °C, the solid - liquid ratio is 1:(3 - 5), the pressure is 0.5 - 1.5 Mpa, the extraction time is 1 - 1.5 h, the extraction times are 2 - 5 times, and butane is evaporated at 55 - 60 °C after extraction.

11. The method according to claim 4, wherein In step (3), the subcritical extraction solvent is butane, the extraction temperature is 40 - 50 °C, the solid - liquid ratio is 1:(3 - 5), the pressure is 0.5 - 1.5 Mpa, the extraction time is 1 - 1.5 h, the extraction times are 2 - 5 times, and butane is evaporated at 55 - 60 °C after extraction.

12. The method according to claim 6, wherein In step (3), the subcritical extraction solvent is butane, the extraction temperature is 40 - 50°C, the ratio of material to liquid is 1:(3 - 5), the pressure is 0.5 - 1.5 Mpa, the extraction time is 1 - 1.5 h, the number of extraction times is 2 - 5 times, and after extraction, butane is evaporated at 55 - 60°C.

13. A capsanthin product, characterized in that, Prepared by the method according to any one of claims 1 - 12.

14. The capsanthin product according to claim 13, wherein, In the capsanthin product, the trans-capsanthin accounts for 45 - 60% of the total carotenoids.

15. Use of the capsanthin product according to claim 13 or 14 in the preparation of feed.

16. A feed additive, characterized in that, Comprising the capsanthin product according to claim 13 or 14.