CN101879428A - Method for preparing carotenoid microcapsules with controllable isomer proportion - Google Patents
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Abstract
The invention discloses a method for preparing carotenoid microcapsules with controllable isomer proportion, which comprises the following steps of: adsorbing the single isomer of carotenoid with a stationary phase in a chromatographic column; taking the stationary phase out, adding the stationary phase into an autoclave according to required proportion and drying the stationary phase; introducing supercritical fluid to fully dissolve the isomer adsorbed by the stationary phase; after filtering, quickly releasing the solution above aqueous solution which contains an antioxidant and a protective colloid under reduced pressure in a spraying mode, and simultaneously controlling the emulsification temperature to be between 40 and 60 DEG C; and homogenizing and emulsifying for 5 to 30 minutes and then performing spray drying to obtain the finished product of the microcapsules. The method has the advantages that: 1) the particle size of the carotenoid reaches 0.04 to 0.6mu m and the bioavailability is high; 2) the proportion of the main isomer of any type of carotenoid can be controlled as required; 3) the product purity is high and solvent residue is avoided; and 4) the configuration of the isomer in the product can be effectively ensured. The method is particularly suitable for preparing carotenoid products as required, which have the controllable isomer proportion and can be applied to different fields, so that the physiological functions of the carotenoid are maximized.
Description
Technical field
The present invention relates to a kind of preparation method of carotenoid microcapsules, particularly relate to the preparation method of the controlled carotenoid microcapsules of a kind of isomer proportion.
Background technology
Carotenoid (Carotenoids) extensively is present in occurring in nature, and its most important representative is beta carotene, astaxanthin, lycopene and canthaxanthin.These materials generally are used for fields such as food, cosmetics, feed and medical industry as nutrition fortifier and colouring agent.Carotenoid is water insoluble, and solubility is also very little in oil, and all very responsive to light, heat and oxygen, can't directly use.Generally all need carotenoid with fine particulate, and protect, make dosage forms such as microcapsules with protective colloid.Carotenoid can significantly improve bioavilability after preparationization, improve coloring effect and reduce consumption.
In addition, isomerization reaction very easily takes place in carotenoid, except that alltrans, 5 suitable-, 9 suitable-and 13 suitable-isomers are the topmost several cis-isomers of carotenoid.Provitamin A activity and oxidation resistance that it is generally acknowledged cis-isomer are lower than alltrans, so most of carotenoid product is all pursued higher alltrans ratio.But carotenoid all is to exist with different isomerization body ratio in organism, and constantly there are some researches show, there are a lot of advantages in the cis-isomer of carotenoid than alltrans: the oxidation resistance of the cis-isomer of beta carotene, lycopene and astaxanthin etc. is better than alltrans isomers [J.Agric.Food Chem.2002 in some antioxidation in vitro experiment, 50,221-226; Biochem.Biophys.Res.Commun.2007,357,187-193]; 9 suitable-canthaxanthins have the pro-apoptosis bioactivity higher than alltrans [Free Radical Res.2009,43,100-105] to the THP-1 macrophage; And the cis beta carotene is digested and assimilated [J.Agric.Food Chem.2006,54,2780-2785] than alltrans is easier in the Caco-2 cell model; The solubility of cis-isomer will be significantly greater than the alltrans isomers.
Above result of study shows that the carotenoid product for preparing specific isomer proportion is more meaningful than simple preparation high-all-trans-carotenoid product.But wherein there are a lot of technological difficulties in this, mainly is that the separation of constant isomers is difficult; Successfully also be difficult to stable existence even separate, processing procedure can impel individual isomer that isomerization reaction takes place fast for a long time.Microcapsules can effectively be protected carotenoid as a kind of good dosage form, suppress the generation of isomerization reaction and other metamorphic reaction.Therefore theoretically, as long as separate isomers of carotenoids, and in the preparation process, shorten the processing time, reduce temperature and suppress the oxygen influence, under the situation that guarantees particle diameter, the carotenoid of specific isomer proportion is made microcapsules, just can realize preparing as required the controlled carotenoid product of isomer proportion that is applicable to different field, with the physiological function maximization of carotenoid.But how to give specific implementation, do not see relevant report so far as yet.
Have before this much about preparing the report of high alltrans or high-cis carotenoid product, but never relate to the preparation method of the controlled carotenoid product of isomer proportion.
Report about the preparation method of carotenoid microcapsules mainly contains following several:
WO91/06292 and WO94/19411 have introduced and have used colloid mill that beta carotene is ground to form the particulate of 2～10 μ m, and drying is made the carotenoid powder of aqueous dispersion then.But the method efficient is low, energy consumption is big, and the carotenoid particle diameter is difficult to reach 1 μ m, and this processing procedure is very easily impelled isomers of carotenoids generation isomery.
US3998753 has put down in writing the dispersible carotenoid preparation method of a kind of water, and wherein the particle diameter of carotenoid is less than 1 μ m.This method is made into carotenoid and other additive the solution of organic solvent earlier, joins then in the aqueous solution that contains gelatin, dispersant, stabilizing agent, makes system formation emulsion through high speed shear; Remove organic solvent and spray-drying obtains required product.Obviously the long duration of action of organic solvent can't guarantee the specific isomer proportion of carotenoid, and the application of the restricted carrotene product of dissolvent residual meeting.
The method of the carotenoid powder of the preparation aqueous dispersion that EP0065193 (or US4522743) is put down in writing; be that carotenoid was dissolved in 10 seconds in the mixable solvent of volatile water in 50～200 ℃; descend and the aqueous solution rapid mixing that contains protecting colloid in 0～50 ℃ then; carotenoid promptly with the size dispersion of＜0.5 μ m in protecting colloid, remove solvent and dry carotenoid powder.This technology needs to carry out under high temperature (170～200 ℃), and carotenoid has reached molten condition under this temperature, can change the mixture of cis-trans-isomer rapidly into, uncontrollable at all isomer proportion.
On these patent bases, we also apply for a series of patents successively, comprise a kind of preparation method (patent publication No. CN1836652A) of water-dispersed carotenoid powder of application in 2005 and the preparation method (patent publication No. CN101549273A) of the high-all-trans-carotenoid microcapsules of the nano-dispersed of applying in 2009.These patents and some other patent all need to use organic solvent, the dissolving of solvent, displacement and evaporation process all can promote the carrying out of carotenoid isomerization reaction, and high boiling solvent (as grease) is because the too high suitable back mixing compound that directly makes carotenoid change fixed proportion into of treatment temperature, and this high boiling solvent can be present in the microcapsules always, influences the stability of carotenoid.
Based on above reason, conventional solvent can not be used to prepare the controlled carotenoid microcapsules of isomer proportion.Supercritical fluid is because its unique character is widely used in every field.For example supercritical liquid extraction technique is emerging one extraction of food industry and isolation technics.It utilizes supercritical fluid to make extractant, extraction from the liquid or solid material, separation and purifying active ingredient.Compare with traditional chemical solvent extraction, its superiority is no chemical solvent consumption and activity residual, pollution-free, that avoid at high temperature hot deterioration of extract, protection physiological activator.Technology is simple, and energy consumption is low, and extractant is nontoxic, easily reclaims; When the preparation carotenoid formulation, can utilize supercritical fluid to handle at normal temperatures.Under certain pressure, carotenoid may be dissolved in the supercritical fluid, and the step by similar solvent method obtains product.Difference is, the process of the removal solvent that the solvent method needs are complicated returns to normal pressure and need only pressure in the first supercritical processing method, and fluid will be vaporized and be separated with product naturally; Simultaneously, can obtain the dispersion of different-grain diameter by selecting different supercritical fluids, the scope that can screen is very big.
About utilizing supercritical fluid to prepare the method for carotenoid microcapsules, mainly contain following several:
CN1233169A (or WO9816204) has reported two kinds of treatment with supercritical fluid technologies: A technology is earlier carotenoid to be dissolved under HTHP in the overcritical dimethyl ether, and explosive decompression obtains Powdered carotenoid particle then; B technology is earlier carotenoid to be dissolved under HTHP in the subcritical or postcritical Compressed Gas, then this solution is scattered in other batching, makes powder preparation after the Compressed Gas in this mixed liquor being removed again.A technology can't make the carotenoid stable existence owing to do not make preparation; Two kinds of technologies of A and B are because treatment temperature too high (being respectively 40～150 ℃ and 50～200 ℃ by claims), although improved the solubility of supercritical fluid, but promoted the isomerization of carotenoid simultaneously, can not be used to prepare the controlled carotenoid product of isomer proportion; Make batching such as carotenoid, supercritical fluid and polyethylene glycol form dispersion liquid in the B technology, and directly spraying obtains the coprecipitate of carotenoid and batching, this coprecipitate is different from microcapsules, can't guarantee the storage stability of carotenoid.
US6056791 has also reported a kind of technology, under certain pressure, carotenoid is mixed with supercritical fluid, contains the solution of 5%-90% supercritical fluid up to formation.The fusing point of selected supercritical fluid hangs down 40 ℃ at least than the fusing point of carotenoid.Then temperature is adjusted to apart from the shooting flow bulk melting point more than 50 ℃, and pressure is reduced to atmospheric pressure.Supercritical fluid gasifies rapidly with this understanding, and the carotenoid particle grain size can reach 0.7 μ m-5 μ m simultaneously.Same because treatment temperature is high and do not make microcapsules, cause the ratios of the isomers regular meeting of carotenoid to change.
Mention among the DE2943267, beta carotene is dissolved in explosive decompression behind the supercritical fluid, obtain the fine grained beta carotene, add other batching again and make solid chemicals.Owing to do not make microcapsules, the beta carotene isomers can't stable existence, and the high processing temperature can promote the beta carotene isomerization simultaneously.
Summary of the invention
The objective of the invention is problem, the preparation method of the controlled carotenoid microcapsules of a kind of isomer proportion is provided at above-mentioned existence.
The preparation method of the carotenoid microcapsules that isomer proportion of the present invention is controlled is: separate carotenoid in chromatographic column, with the phase wash-out that flows, make isomers be adsorbed in fixedly phase; Take out mutually adsorbing the fixing of individual isomer, be added in the autoclave, logical high pure nitrogen 10～30 minutes and emptying, fully dry fixedly phase in required ratio; Feed supercritical fluid under the high pressure low temperature condition, isomers during fully dissolving is fixed mutually 1～10 minute, discharge with the Sprayable explosive decompression above the aqueous solution of solution through containing antioxidant and protecting colloid behind the ultra-fine strainer filtering, controlling emulsifying temperature simultaneously is 40 ℃～60 ℃, emulsifying 5～30 minutes; The spray-dried controlled carotenoid microcapsules of isomer proportion that obtains of emulsion.The present invention uses the purpose of ultra-fine strainer filtering to be fixedly phase of filtering, so the order number of described ultra-fine filter screen be there is no unified demand, can suitably adjust according to the fixing order number of phase.
The present invention has no particular limits described antioxidant and protecting colloid; existing antioxidant and protecting colloid all are applicable to the present invention, are that Chinese patent, the application number of ZL200710067317.7 is that 200910097064.7 Chinese patent application and application number are 200910097063.2 the disclosed antioxidant of Chinese patent application and colloid etc. as the patent No..
The isomers of described carotenoid comprises alltrans-carotenoid, 5 suitable-carotenoid, 9 suitable-carotenoid and 13 suitable-carotenoid.Carotenoid is beta carotene, astaxanthin, lycopene or canthaxanthin.Flow is the mixture of mixture, n-hexane and acetone of benzinum, n-hexane, benzinum and acetone or the mixture of n-hexane and ether mutually.Fixing is magnesia, silica gel, calcium carbonate or calcium hydroxide mutually.The high pressure low temperature condition be pressure between 20～50MPa, temperature is between 20～60 ℃.Supercritical fluid is dimethyl ether or carbon dioxide.The carotenoid particle diameter is 0.04～0.6 μ m in the carotenoid microcapsules, and in peak area percentage in the liquid chromatogram, individual isomer accounts for 0.5%～99% of every kind of carotenoid total amount.
Advantage of the present invention is: 1) utilize Sprayable that the carotenoid explosive decompression is discharged in the emulsion, the carotenoid particle diameter reaches 0.04～0.6 μ m, bioavilability height; 2) ratio that can control arbitrary main isomer comprises carotenoid on demand is 0.5%～99%; 3) whole technology requires height, makes the carotenoid product of high-purity, no solvent residue.4) the entire process technological temperature is low, the time short, can guarantee the configuration of isomers as far as possible, avoids the isomerization in the processing procedure.Particularly, individual isomer is directly used to be adsorbed in the fixing mode that goes up mutually among the present invention, is very beneficial for guaranteeing the configuration of isomers.Its reason is that isomers is adsorbed in the fixing effect that is subjected to hydrogen bond and Van der Waals force etc. when going up mutually, so two key is difficult to upset, isomers is difficult for isomerization.
The specific embodiment
The present invention with the phase wash-out that flows, makes isomers be adsorbed in fixedly phase by separate carotenoid in chromatographic column; Take out mutually adsorbing the fixing of individual isomer, be added in the autoclave, logical high pure nitrogen 10～30 minutes and emptying, fully dry fixedly phase in required ratio; Feed supercritical fluid under the high pressure low temperature condition, isomers during fully dissolving is fixed mutually 1～10 minute, discharge with the Sprayable explosive decompression above the aqueous solution of solution through containing antioxidant and protecting colloid behind the ultra-fine strainer filtering, controlling emulsifying temperature simultaneously is 40 ℃～60 ℃, emulsifying 5～30 minutes; The spray-dried controlled carotenoid microcapsules of isomer proportion that obtains of emulsion.The present invention is described in detail below in conjunction with embodiment.Below if no special instructions, the percentage composition in the specification all refers to peak area percentage composition in the liquid chromatogram.
Embodiment 1
In industrial chromatographic column, load calcium hydroxide, add the beta carotene solution that is rich in cis-isomer then, with the benzinum wash-out, treat that the about 100kg of calcium hydroxide that will adsorb 9 suitable-beta carotenes after bands of a spectrum separate fully takes out, add in the autoclave, logical high pure nitrogen 30 minutes and emptying under the 500kPa, fully dry hydrogen calcium oxide; Autoclave is heated to 20 ℃; it is 50MPa that dimethyl ether (cosmetics-stage) is pumped in the autoclave until pressure; dissolved 10 minutes; solution directly discharges in the decompression of the prewired aqueous solution that contains antioxidant and protecting colloid (containing 300g gelatin, 100g sucrose, 10gVC sodium salt and 2500ml water) top with Sprayable behind ultra-fine strainer filtering, controls emulsifying temperature simultaneously and be 40 ℃ and emulsifying 5 minutes.The spray-dried microcapsules that obtain containing beta carotene 12% of emulsion, the beta carotene volume average particle size is 0.6 μ m by analysis, 9 along isomer comprises 99%.
Embodiment 2
In industrial chromatographic column, load magnesia, add the lycopene solution that is rich in cis-isomer then, with benzinum/acetone wash-out, treat that the about 120kg of magnesia that will adsorb 5 suitable-lycopenes after bands of a spectrum separate fully takes out, add in the autoclave, logical high pure nitrogen 10 minutes and emptying under the 500kPa, abundant dry magnesia; Autoclave is heated to 60 ℃; it is 20MPa that carbon dioxide is pumped in the autoclave until pressure; dissolved 1 minute; solution directly discharges in the decompression of the prewired aqueous solution that contains antioxidant and protecting colloid (containing 300g gelatin, 100g sucrose, 10gVC sodium salt and 2500m1 water) top with Sprayable behind ultra-fine strainer filtering, controls emulsifying temperature simultaneously and be 60 ℃ and emulsifying 30 minutes.The spray-dried microcapsules that obtain containing lycopene 11.3% of emulsion, the lycopene volume average particle size is 0.04 μ m by analysis, 5 along isomer comprises 99%, alltrans isomer comprises 0.5%.
Embodiment 3
In industrial chromatographic column, load silica gel, add the astaxanthin solution that is rich in cis-isomer then, with the n-hexane/acetone wash-out, treat that the about 90kg of silica gel that will adsorb 13 suitable-astaxanthins after bands of a spectrum separate fully takes out, add in the autoclave, logical high pure nitrogen 20 minutes and emptying under the 400kPa, fully dry silica gel; Autoclave is heated to 30 ℃; it is 40MPa that carbon dioxide is pumped in the autoclave until pressure; dissolved 5 minutes; solution directly discharges in the decompression of the prewired aqueous solution that contains antioxidant and protecting colloid (containing 300g gelatin, 100g sucrose, 10gVC sodium salt and 2500ml water) top with Sprayable behind ultra-fine strainer filtering, controls emulsifying temperature simultaneously and be 40 ℃ and emulsifying 10 minutes.The spray-dried microcapsules that obtain astaxanthin-containing 9.8% of emulsion, the astaxanthin volume average particle size is 0.1 μ m by analysis, 13 along isomer comprises 99%, alltrans isomer comprises 0.7%.
Embodiment 4
In industrial chromatographic column, load calcium carbonate, add the canthaxanthin soln that is rich in cis-isomer then, with n-hexane/ether wash-out, treat that the about 105kg of calcium carbonate that will adsorb 13 suitable-canthaxanthins after bands of a spectrum separate fully takes out, add in the autoclave, logical high pure nitrogen 25 minutes and emptying under the 600kPa, abundant dry calcium carbonate; Autoclave is heated to 40 ℃; it is 45MPa that dimethyl ether (cosmetics-stage) is pumped in the autoclave until pressure; dissolved 8 minutes; solution directly discharges in the decompression of the prewired aqueous solution that contains antioxidant and protecting colloid (containing 300g gelatin, 100g sucrose, 10gVC sodium salt and 2500ml water) top with Sprayable behind ultra-fine strainer filtering, controls emulsifying temperature simultaneously and be 45 ℃ and emulsifying 15 minutes.The spray-dried microcapsules that obtain containing canthaxanthin 9.4% of emulsion, the canthaxanthin volume average particle size is 0.3 μ m by analysis, 13 along isomer comprises 93%, alltrans isomer comprises 5.7%.
Embodiment 5
In industrial chromatographic column, load magnesia, add the lycopene solution that is rich in cis-isomer then, with the n-hexane wash-out, the about 40kg of magnesia, the about 35kg of magnesia of absorption 5 suitable-lycopenes, the about 10kg of magnesia of absorption 9 suitable-lycopenes, the about 15kg of magnesia of absorption 13 suitable-lycopenes that treat will adsorb after bands of a spectrum separate fully alltrans-lycopene take out, add in the autoclave, logical high pure nitrogen 25 minutes and emptying under the 700kPa, abundant dry magnesia; Autoclave is heated to 45 ℃; it is 50MPa that carbon dioxide is pumped in the autoclave until pressure; dissolved 8 minutes; solution directly discharges in the decompression of the prewired aqueous solution that contains antioxidant and protecting colloid (containing 300g gelatin, 100g sucrose, 10gVC sodium salt and 2500ml water) top with Sprayable behind ultra-fine strainer filtering, controls emulsifying temperature simultaneously and be 50 ℃ and emulsifying 25 minutes.The spray-dried microcapsules that obtain containing lycopene 9.4% of emulsion, the lycopene volume average particle size is 0.25 μ m by analysis, alltrans isomer comprises 38%, 5 is along isomer comprises 37%, 9 suitable isomer comprises 9.5%, 13 suitable isomer comprises 14%.
Embodiment 6
In industrial chromatographic column, load silica gel, add canthaxanthin soln then, with the n-hexane wash-out, treat that the about 100kg of silica gel that will adsorb alltrans-canthaxanthin after bands of a spectrum separate fully takes out, add in the autoclave logical high pure nitrogen 20 minutes and emptying under the 800kPa, fully dry silica gel; Autoclave is heated to 40 ℃; it is 30MPa that dimethyl ether (cosmetics-stage) is pumped in the autoclave until pressure; dissolved 10 minutes; solution directly discharges in the decompression of the prewired aqueous solution that contains antioxidant and protecting colloid (containing 300g gelatin, 100g sucrose, 10gVC sodium salt and 2500ml water) top with Sprayable behind ultra-fine strainer filtering, controls emulsifying temperature simultaneously and be 50 ℃ and emulsifying 20 minutes.The spray-dried microcapsules that obtain containing canthaxanthin 9.9% of emulsion, the lycopene volume average particle size is 0.3 μ m by analysis, alltrans isomer comprises 99%.
Embodiment 7
In industrial chromatographic column, load magnesia, add beta carotene solution then, with the benzinum wash-out, treat to adsorb after bands of a spectrum separate fully that the about 100kg of magnesia of content full cis-beta-carotene, the about 0.4kg of magnesia of absorption 9 suitable-beta carotenes take out, add in the autoclave, logical high pure nitrogen 25 minutes and emptying under the 500kPa, fully dry hydrogen calcium oxide; Autoclave is heated to 27 ℃; it is 43MPa that dimethyl ether (cosmetics-stage) is pumped in the autoclave until pressure; dissolved 9 minutes; solution directly discharges in the decompression of the prewired aqueous solution that contains antioxidant and protecting colloid (containing 300g gelatin, 100g sucrose, 10gVC sodium salt and 2500ml water) top with Sprayable behind ultra-fine strainer filtering, controls emulsifying temperature simultaneously and be 45 ℃ and emulsifying 15 minutes.The spray-dried microcapsules that obtain containing beta carotene 10.2% of emulsion, the beta carotene volume average particle size is 0.5 μ m by analysis, alltrans isomer comprises 98.8%, 9 is along isomer comprises 0.5%.
Embodiment 8
In industrial chromatographic column, load silica gel, add the astaxanthin solution that is rich in cis-isomer then, with the benzinum wash-out, the about 50kg of silica gel, the about 20kg of silica gel of absorption 9 suitable-astaxanthins, the about 30kg of silica gel of absorption 13 suitable-astaxanthins that treat will adsorb after bands of a spectrum separate fully alltrans-astaxanthin take out, add in the autoclave, logical high pure nitrogen 20 minutes and emptying under the 700kPa, fully dry silica gel; Autoclave is heated to 40 ℃; it is 45MPa that carbon dioxide is pumped in the autoclave until pressure; dissolved 10 minutes; solution directly discharges in the decompression of the prewired aqueous solution that contains antioxidant and protecting colloid (containing 300g gelatin, 100g sucrose, 10gVC sodium salt and 2500ml water) top with Sprayable behind ultra-fine strainer filtering, controls emulsifying temperature simultaneously and be 50 ℃ and emulsifying 25 minutes.The spray-dried microcapsules that obtain astaxanthin-containing 10.3% of emulsion, the astaxanthin volume average particle size is 0.5 μ m by analysis, alltrans isomer comprises 54%, 9 is along isomer comprises 19%, 13 suitable isomer comprises 26%.
Embodiment 9
In industrial chromatographic column, load magnesia, add the lycopene solution that is rich in cis-isomer then, with the n-hexane wash-out; In another industrial chromatographic column, load calcium carbonate, add the canthaxanthin soln that is rich in cis-isomer then, with n-hexane/ether wash-out; The about 35kg of magnesia, the about 15kg of magnesia of absorption 9 suitable-lycopenes, the about 30kg of calcium carbonate of absorption alltrans canthaxanthin, the about 20kg of calcium carbonate of absorption 13 suitable-canthaxanthins that treat will adsorb after bands of a spectrum separate fully 5 suitable-lycopenes take out, add in the autoclave, logical high pure nitrogen 30 minutes and emptying under the 700kPa, fully dry fixedly phase; Autoclave is heated to 50 ℃; it is 50MPa that dimethyl ether is pumped in the autoclave until pressure; dissolved 10 minutes; solution directly discharges in the decompression of the prewired aqueous solution that contains antioxidant and protecting colloid (containing 300g gelatin, 100g sucrose, 10gVC sodium salt and 2500ml water) top with Sprayable behind ultra-fine strainer filtering, controls emulsifying temperature simultaneously and be 50 ℃ and emulsifying 30 minutes.The spray-dried microcapsules that obtain containing lycopene 4.8%, canthaxanthin 5.1% of emulsion, lycopene and canthaxanthin volume average particle size are 0.6 μ m by analysis, 5 along isomer comprises 72%, 9 suitable isomer comprises 27.5% in the lycopene, alltrans isomer comprises 63%, 13 suitable isomer comprises 36% in the canthaxanthin.
Claims (8)
1. the preparation method of the controlled carotenoid microcapsules of an isomer proportion is characterized in that may further comprise the steps:
1) in chromatographic column, separates carotenoid,, make the isomers of carotenoid be adsorbed in fixedly phase with the phase wash-out that flows;
2) will adsorb the fixing of individual isomer and take out mutually, be added in the autoclave, logical high pure nitrogen 10～30 minutes and emptying, fully dry fixedly phase in required ratio;
3) feed supercritical fluid under the high pressure low temperature condition, isomers during fully dissolving is fixed mutually 1～10 minute, discharge with the Sprayable explosive decompression above the aqueous solution of solution through containing antioxidant and protecting colloid behind the ultra-fine strainer filtering, controlling emulsifying temperature simultaneously is 40 ℃～60 ℃, emulsifying 5～30 minutes;
4) the spray-dried controlled carotenoid microcapsules of isomer proportion that obtains of emulsion.
2. the preparation method of the carotenoid microcapsules that isomer proportion according to claim 1 is controlled is characterized in that described flow mutually is the mixture of mixture, n-hexane and the acetone of benzinum, n-hexane, benzinum and acetone or the mixture of n-hexane and ether.
3. the preparation method of the carotenoid microcapsules that isomer proportion according to claim 1 is controlled is characterized in that described fixing be mutually magnesia, silica gel, calcium carbonate or calcium hydroxide.
4. the preparation method of the carotenoid microcapsules that isomer proportion according to claim 1 is controlled, it is characterized in that described high pressure low temperature condition be pressure between 20～50MPa, temperature is between 20～60 ℃.
5. the preparation method of the carotenoid microcapsules that isomer proportion according to claim 1 is controlled is characterized in that, described supercritical fluid is dimethyl ether or carbon dioxide.
6. according to the preparation method of the controlled carotenoid microcapsules of the described isomer proportion of arbitrary claim in the claim 1 to 5, it is characterized in that the isomers of described carotenoid comprises alltrans-carotenoid, 5 suitable-carotenoid, 9 suitable-carotenoid and 13 suitable-carotenoid.
7. according to the preparation method of the controlled carotenoid microcapsules of the described isomer proportion of arbitrary claim in the claim 1 to 5, it is characterized in that described carotenoid is beta carotene, astaxanthin, lycopene or canthaxanthin.
8. according to the preparation method of the controlled carotenoid microcapsules of the described isomer proportion of arbitrary claim in the claim 1 to 5, it is characterized in that the carotenoid particle diameter is 0.04～0.6 μ m in the described carotenoid microcapsules, in peak area percentage in the liquid chromatogram, individual isomer accounts for 0.5%～99% of every kind of carotenoid total amount.
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| WO2015003536A1 (en) | 2013-07-09 | 2015-01-15 | 浙江新维普添加剂有限公司 | Method for preparing oil-dispersible carotenoid preparation |
| CN105367369A (en) * | 2014-08-22 | 2016-03-02 | 南京生矶坊生物工程有限公司 | Preparation method of stable cis-lycopene |
| CN109513460A (en) * | 2018-11-20 | 2019-03-26 | 扬州大学 | A kind of synthetic method of beta carotene degradation catalyst |
| CN115812960A (en) * | 2022-11-09 | 2023-03-21 | 黑龙江八一农垦大学 | Preparation method of oil-based high-solubility non-oxygen-containing carotenoid |
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| CN105367369A (en) * | 2014-08-22 | 2016-03-02 | 南京生矶坊生物工程有限公司 | Preparation method of stable cis-lycopene |
| CN105367369B (en) * | 2014-08-22 | 2017-06-20 | 南京生矶坊生物工程有限公司 | A kind of preparation method of the All-cislycopene of stabilization |
| CN109513460A (en) * | 2018-11-20 | 2019-03-26 | 扬州大学 | A kind of synthetic method of beta carotene degradation catalyst |
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