CN113575945B - Preparation method of nanoscale all-trans carotenoid dry powder - Google Patents

Preparation method of nanoscale all-trans carotenoid dry powder Download PDF

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CN113575945B
CN113575945B CN202110816043.7A CN202110816043A CN113575945B CN 113575945 B CN113575945 B CN 113575945B CN 202110816043 A CN202110816043 A CN 202110816043A CN 113575945 B CN113575945 B CN 113575945B
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carotenoid
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polyphenol
colloid
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CN113575945A (en
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龚旭
刘英瑞
张涛
李莉
高洪坤
刘伟杰
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Wanhua Chemical Group Co Ltd
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
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    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
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    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/10—Foods or foodstuffs containing additives; Preparation or treatment thereof containing emulsifiers
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    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Abstract

The invention provides a preparation method of nanoscale all-trans carotenoid dry powder, which comprises the following steps: 1) Dissolving high all-trans carotenoid with the content of more than 97% in an organic solvent to form a solution, mixing the solution with phosphate aqueous solution with the concentration of 0.1-0.5%, and obtaining carotenoid crystal dispersion liquid with the solid content of 5-20% through centrifugal phase separation; 2) Mixing the polyphenol-vegetable protein composite colloid, an emulsifying agent, sugar and water to obtain a protective colloid water phase; 3) Mixing carotenoid dispersion liquid with water phase to obtain emulsion; 4) And (3) carrying out spray drying on the emulsion to obtain carotenoid dry powder. The invention carries out induced precipitation on carotenoid through phosphate aqueous solution, solves the problems of loss of active ingredients, low content and use of high-toxicity halogenated hydrocarbon solvent in a high-temperature dissolution method; the polyphenol-vegetable protein complex colloid avoids the use of traditional antioxidants; the content of all-trans in the obtained dry powder can be kept above 94%, and the dry powder has higher bioavailability and water-soluble stability.

Description

Preparation method of nanoscale all-trans carotenoid dry powder
Technical Field
The invention relates to a preparation method of nanoscale all-trans carotenoid dry powder, belonging to the field of preparation of nutritional chemicals.
Background
Carotenoids are highly unsaturated compounds having a plurality of conjugated double bonds and methyl branches, which are widely found in nature and important representative substances are beta-carotene, canthaxanthin, lycopene, astaxanthin, apoester, lutein, etc., which have characteristic colors ranging from yellow to red. These substances are widely used as nutrients and colorants in the food, feed, cosmetic and pharmaceutical industries. In addition, part of the carotenoid can be used as a vitamin A active precursor and has important physiological functions for animals. However, carotenoids are poorly soluble in water and most organic solvents due to their unique chemical structure, and are sensitive to light, temperature, oxygen, and difficult to apply directly as products. Therefore, in order to improve the application value of carotenoids in practical production, it is necessary to process the carotenoid active ingredient into a formulation product which can be stored for a long period of time, prevent oxidation, and have a certain bioavailability.
In order to achieve the aim that the carotenoid active ingredient is easily absorbed in the animal body, it is required to reduce the particle size of the active ingredient, and particularly when the particle size is reduced to the nanometer level, the carotenoid has high bioavailability, and at present, some literature reports have been made on the preparation method of the carotenoid preparation.
European patent EP0239086 describes a process for the preparation of carotenoid emulsion formulations, in which carotenoids are dissolved in an oil, and a mixture of long-chain fatty acid esters with ascorbate and water-soluble starch is used to stabilize the oil phase, and finally the product has a carotenoid content of 0.1% to 2%, a very low carotenoid content and low practical value.
WO/2010/040683 describes a method for the preparation of a ready-to-use emulsion using a glycerol-water mixture as protective colloid, adding modified starch to swell under heating, then mixing the aqueous phase with a carotenoid oil melt, and homogenizing at high speed and high pressure to a water-dispersible emulsion. The method accelerates the oxidation and deterioration process of carotenoid by using the traditional high-temperature melting method, and the isomer content is changed, so that the obtained emulsion product can not be stored for a long time.
Although the carotenoid emulsion preparation has simple preparation process, the emulsion preparation has poor product stability, the biological activity in the effective components is not high, and the bioavailability of the product is low and the applicability is poor. In order to modify the stability of carotenoid formulation products, it is necessary to use different embedding agents to prepare the emulsion as a stable dry powder product.
US5364563 describes a process for the preparation of a powdered preparation of carotenoids by mixing carotenoids with vegetable oils having boiling points exceeding 200 ℃ to form a suspension, then subjecting the suspension to high temperature dissolution by steam at temperatures up to 200 ℃, mixing the water and oil phases by a homogenizer to obtain an emulsion, and then spray drying the emulsion by a fluidized bed loaded with starch to obtain the product. The carotenoid content loss is large in the high-temperature heating process, and the final all-trans content is only 70%. In addition, the use of superheated steam at high temperature and high pressure requires expensive equipment, and the equipment operation requires high demands, and the process is complicated and the productivity is not high.
US5827539 describes the milling of an oil dispersion comprising carotenoid particles using a ball mill such that the average diameter of undissolved carotenoid particles in the dispersion is less than 1 micron. The aqueous embedding mixture is formed by dissolving starch as embedding agent, sugar and antioxidant in water. The ground carotenoid-oil dispersion is then emulsified with the aqueous phase. Finally, the resulting emulsion is dried to produce a powder, which is encased in a protective starch matrix. The method has the advantages that the grinding time is long, the trans isomer content of carotenoid is drastically reduced due to the high temperature generated by grinding, and the maximum carotenoid content produced by the method is 5 percent. In addition, the method has high energy consumption, and the used equipment is not suitable for mass production.
To avoid the use of oils or fats as carotenoid solvents, US patent 3998753 describes a process for preparing water-dispersible carotenoid powders wherein the particle size of the carotenoids is less than 1 μm, which comprises (a) dissolving the carotenoids and antioxidants in a halogenated aliphatic hydrocarbon solvent selected from chloroform, carbon tetrachloride and methylene chloride; (b) Forming an aqueous solution of a water-soluble carrier composition which is gelatin, a preservative and an emulsifier, and adjusting the pH of said solution to 10-11; (c) Mixing (a) and (b) by high-speed shearing to form emulsion, and then spray drying to prepare carotenoid powder.
In European publication EP0065193 or corresponding U.S. Pat. No. 4522743, a continuous process for the preparation of finely divided carotenoid and retinoid powders is described, wherein the particle size of the carotenoid or retinoid is substantially below 0.5 μm. The process comprises the following steps: the carotenoid or retinoid is dissolved in a volatile organic solvent at a high temperature of about 200 ℃ for less than 10 seconds. Then, by rapid mixing with an aqueous solution of a swellable colloid at 50 ℃, carotenoids or retinoids are immediately precipitated from the resulting molecular dispersion solution in a colloidally dispersed form, and finally the dispersion is dried to obtain a powder formulation.
The organic solvent method and the high-temperature dissolution method both need to use high temperature to solve the problem of poor solubility of carotenoid, and the high-temperature dissolution process has high requirements on equipment, high energy consumption and no industrialization advantage. And a large amount of solvent is removed from the protective colloid system, so that the process time is longer, the carotenoid content and the all-trans isomerism content with poor stability are obviously reduced, the particle size is difficult to control at the nanometer level, and the bioavailability is poor.
Disclosure of Invention
The invention aims to provide a preparation method of nano-dispersed carotenoid dry powder which is easy for industrial production, and meanwhile, the method can keep high content and high content of all-trans isomer and has high bioavailability.
The preparation method of the nanoscale all-trans carotenoid dry powder provided by the invention comprises the following steps of:
1) Mixing carotenoid solid with the total trans content of more than 97% with an organic solvent, dissolving the carotenoid solid under a heating reflux state to obtain a carotenoid solution, slowly dripping the carotenoid solution into a phosphate aqueous solution with a certain concentration to precipitate nanocrystals with the particle size of 50-300 nm, and finally carrying out centrifugal phase separation on the two-phase nanocrystal mixed solution to obtain carotenoid crystal dispersion liquid with the solid content of 5-20%;
2) Mixing polyphenol-plant protein composite colloid, an emulsifying agent, sugar and warm deionized water, and shearing for a period of time by a high-speed shearing machine to obtain a protective colloid water phase mixture;
3) Mixing the carotenoid crystal dispersion liquid with the protective colloid water phase mixture, and shearing for a period of time by a high-speed shearing machine to obtain a stably dispersed carotenoid nanoemulsion, wherein the residual organic solvent is removed in the process; the mass ratio of the carotenoid crystal dispersion liquid to the protective colloid water phase mixture is 0.1-0.4:1;
4) And (3) carrying out spray drying on the stably dispersed carotenoid nanoemulsion, and controlling the air inlet temperature, the emulsion temperature, the atomizer rotating speed and the feeding flow parameters during spraying to obtain carotenoid dry powder with the content of 5% -40%, wherein the content of all-trans carotenoid isomer is more than 94%.
In the method of the present invention, the carotenoid of step 1) is selected from the group consisting of beta-carotene, canthaxanthin, lycopene, astaxanthin, apoester, lutein and the like.
In the method of the invention, the organic solvent in the step 1) is selected from one or more of ethyl formate, ethyl acetate, methyl tertiary butyl ether and isopropyl acetate.
In the process of the present invention, in step 1), the mass ratio of the organic solvent to the carotenoid is 10 to 50:1, preferably 10 to 20:1; the dissolution temperature is 50-90 ℃, preferably 60-80 ℃;
the phosphate is one or more of potassium phosphate, potassium pyrophosphate, sodium dihydrogen phosphate, sodium pyrophosphate, calcium pyrophosphate and potassium dihydrogen phosphate; the concentration of the aqueous phosphate solution is 0.1 to 0.5wt%, preferably 0.2 to 0.3wt%;
the drop speed of carotenoid solution is 5-20 ml/min, preferably 8-15 ml/min; the mass ratio of the phosphate aqueous solution to the carotenoid solution is 0.8-4:1, preferably 0.9-2:1.
In the process of the present invention, the carotenoid crystal dispersion obtained in step 1) has a solid content of 5 to 20%, preferably 7 to 10%.
In the method of the invention, the preparation method of the polyphenol-plant protein composite colloid in the step 2) comprises the following steps:
dissolving vegetable protein in water to prepare a vegetable protein solution with the concentration of 1-8 wt%, preferably 1-1.5 wt%;
dissolving polyphenol in water to prepare a polyphenol solution with the concentration of 0.8-2 wt%, preferably 0.9-1.5 wt%; the mass ratio of the vegetable protein solution to the polyphenol solution is 1-1.5: 1, a step of;
the pH of the two solutions is adjusted to be 3.0-7.0 by using 0.1M HCl and 0.1M NaOH respectively, preferably the pH of the plant protein solution is 5.5-6.0, preferably the pH of the polyphenol solution is 5.0-5.5, then the polyphenol solution is added into the plant protein solution dropwise under magnetic stirring or the plant protein solution is added into the polyphenol solution dropwise, the stirring speed is 300-600 rpm, the mixing temperature is 30-40 ℃, and then the polyphenol-plant protein composite colloid is obtained through a freeze drying process.
The polyphenol is one or more of salicylic acid, quinic acid, malic acid, caffeic acid and curcumin. The polyphenol-plant protein composite colloid is one or more of polyphenol-soybean protein, polyphenol-wheat protein, polyphenol-corn protein and polyphenol-peanut protein.
In the method of the invention, the emulsifier in the step 2) is one or more of sorbitan monooleate, polyglycerol monooleate, citric acid ester and ascorbyl palmitate, and the preferred emulsifier is ascorbyl palmitate and/or sorbitan monooleate. The mass ratio of the composite colloid to the emulsifier is 20-60:1, preferably 30-40: 1.
in the method of the invention, the sugar in the step 2) is one or more of sucrose, glucose, sorbitol, mannitol and fructose; the mass ratio of the complex colloid to the sugar is 2-10:1, preferably 4-8:1.
In the method of the invention, the temperature of the deionized water in the step 2) is 30-55 ℃, preferably 45 ℃; the mass ratio of the deionized water to the composite colloid is 4-10:1, preferably 5-8:1.
In the method of the invention, the rotating speed of the high-speed shearing machine in the step 2) is 5000-12000 r/min, preferably 8000-10000 r/min; the shearing time is 5 to 20min, preferably 10 to 15min.
In the method of the invention, the rotating speed of the high-speed shearing machine in the step 3) is 5000-12000 r/min, preferably 9000-10000 r/min; the shearing time is 15 to 40min, preferably 25 to 30min.
In the process of the present invention, the mode of removing the residual organic solvent in step 3) is atmospheric distillation, and reduced pressure distillation may be employed if appropriate, the distillation pressure being 40 to 80kPa, preferably 50 to 60kPa.
In the method of the invention, the inlet air temperature in the step 4) is 100-120 ℃, preferably 110-115 ℃; the emulsion temperature is 40-70 ℃, preferably 50-55 ℃; the rotating speed of the atomizer is 8000-15000 r/min, preferably 10000-12000 r/min; the feed flow is 10 to 30ml/min, preferably 15 to 20ml/min.
The core of the invention is that carotenoid solid is pretreated by adopting an induction precipitation method to obtain nano-level carotenoid nano-dispersion liquid, and the phosphate aqueous solution promotes the precipitation of nanocrystals, so that the preparation of nanoemulsion is more convenient and faster, the problems of loss of active ingredients and low content of the high-temperature dissolution method are solved, meanwhile, the oxidation of carotenoid and the use of high-toxicity halohydrocarbon are avoided, and the industrial production is facilitated. In addition, the polyphenol-plant protein composite colloid is used as a protective colloid, and due to the oxidation resistance of the polyphenol and the emulsifying property of the composite colloid, the use of the traditional antioxidant is avoided, so that the stability of the product is more superior, and the bioavailability is high.
The invention has the beneficial effects that:
the carotenoid content in the carotenoid dry powder prepared by the invention is 5% -40%, the particle size D90 of carotenoid crystals is less than 200nm, and the content of all-trans carotenoid isomers is more than 94%.
Detailed Description
For a better understanding of the technical solution of the present invention, the following examples are further described below, but the present invention is not limited to the following examples.
Example 1
1) 200g of beta-carotene solid with 97% of all-trans content is dissolved in 2kg of ethyl acetate, the dissolution temperature is 80 ℃, then the beta-carotene solution is pumped into 2kg of sodium pyrophosphate aqueous solution with 0.3wt% of concentration by slurry at the flow rate of 10ml/min, and the beta-carotene solution is stood for 40 minutes at room temperature after the addition of the beta-carotene solution is completed. And then separating the upper ethyl acetate phase by centrifugal phase separation to obtain beta-carotene dispersion liquid with the solid content of 9%, wherein the particle size D90 of the beta-carotene crystal is less than 200nm.
2) The salicylic acid-soy protein composite colloid is prepared by the following steps: 1kg of soy protein was dissolved in 50kg of deionized water and the pH was adjusted to 5.5 with 0.1M HCl solution; salicylic acid 0.5kg was dissolved in 50kg deionized water and the pH was adjusted to 5.0 with 0.1M NaOH solution; then under the magnetic stirring, the rotation speed is 300rpm, the soybean protein solution is added into the salicylic acid solution drop by drop, the mixing temperature is ensured to be 30 ℃, and then the salicylic acid-soybean protein composite colloid is obtained through freeze drying.
3) 1.5kg of the prepared salicylic acid-soybean protein composite colloid, 40g of ascorbyl palmitate and 400g of glucose are added into 7.5kg of deionized water at 45 ℃, and the mixture is sheared by a high-speed shearing machine for 10 minutes at a shearing speed of 9000r/min, so as to obtain a composite colloid water phase.
4) Mixing the beta-carotene dispersion liquid with the composite colloid water phase, shearing for 30 minutes by a high-speed shearing machine at the shearing speed of 10000r/min to obtain beta-carotene emulsion, carrying out reduced pressure distillation (the pressure is 50 kPa) in the shearing process to remove a small amount of ethyl acetate solvent, and finally measuring the emulsion particle diameter D90 to be 176nm.
5) The emulsion is dehydrated and dried by a spray drying tower, the air inlet temperature is 110 ℃, the emulsion temperature is 50 ℃, the rotating speed of an atomizer is 10000r/min, and the feeding flow is 15ml/min, so that the beta-carotene dry powder is obtained. Through testing, the content of beta-carotene in the dry powder is 9.1%, the content of all-trans isomer is 94.5%, and the embedding rate is 99.8%. The product is preserved for 6 months at 30 ℃ under the condition of 60% humidity, the content of beta-carotene is 9.0%, and the content of all-trans isomer is 94.4%.
Example 2
1) 200g of canthaxanthin solid with the total trans content of 97.3% is dissolved in 2.1kg of ethyl formate at the dissolution temperature of 60 ℃, then the canthaxanthin solution is pumped into 2.4kg of potassium phosphate aqueous solution with the concentration of 0.32wt% at the flow rate of 12ml/min, and the canthaxanthin solution is stood for 30 minutes at room temperature after the addition of the canthaxanthin solution is completed. Then separating the upper ethyl formate phase by centrifugal phase separation to obtain canthaxanthin dispersion liquid with solid content of 8%, wherein the particle diameter D90 of canthaxanthin crystal is less than 200nm.
2) Quinic acid-zein complex colloids were prepared according to the method of example 1.
1.2kg of the prepared quinic acid-zein composite colloid, 38g of citric acid ester and 385g of sucrose are added into 7kg of deionized water at 45 ℃, and the mixture is sheared for 15 minutes by a high-speed shearing machine at 11000r/min, so as to obtain a composite colloid water phase.
3) Mixing canthaxanthin dispersion liquid with composite colloid water, shearing for 30min by a high-speed shearing machine at 10000r/min to obtain canthaxanthin emulsion, distilling under reduced pressure (pressure is 65 kPa) during shearing to remove a small amount of ethyl formate solvent, and finally measuring emulsion particle diameter D90 of 186nm.
4) The emulsion is dehydrated and dried by a spray drying tower, the air inlet temperature is 120 ℃, the emulsion temperature is 60 ℃, the rotating speed of an atomizer is 10000r/min, and the feeding flow is 20ml/min, so as to obtain the canthaxanthin dry powder. Through testing, the content of canthaxanthin in the dry powder is 10.5%, the content of all-trans isomer is 96.5%, and the embedding rate is 99.9%. The obtained product is preserved for 6 months at 30deg.C under a humidity of 60%, wherein the content of canthaxanthin is 10.1%, and the content of all-trans isomer is 95.0%.
Example 3
1) 200g of aporate solid with the total trans content of 98.0% is dissolved in 2.9kg of isopropyl acetate, the dissolution temperature is 85 ℃, and then the aporate solution is pumped into 2.8kg of potassium pyrophosphate aqueous solution with the concentration of 0.28% by using a slurry at the flow rate of 16ml/min, and the solution is stood for 30 minutes at room temperature after the addition of the aporate solution is completed. And separating the isopropyl acetate phase at the upper layer by centrifugal phase separation to obtain aporate dispersion liquid with the solid content of 7 percent, wherein the particle size D90 of aporate crystals is less than 200nm.
2) Curcumin-wheat protein complex colloid was prepared by the method of example 1.
The prepared curcumin-wheat protein composite colloid is added with 1.03kg, 30g of polyglycerol monooleate and 370g of fructose into 8kg of deionized water at 45 ℃ and sheared for 20 minutes by a high-speed shearing machine, and the shearing speed is 10000r/min, so as to obtain a composite colloid water phase.
3) The aporate dispersion liquid and the composite colloid are mixed, and sheared by a high-speed shearing machine for 25 minutes at the shearing speed of 10000r/min to obtain aporate emulsion, a small amount of isopropyl acetate solvent is removed by reduced pressure distillation (the pressure is 65 kPa) in the shearing process, and finally the emulsion particle diameter D90 is 195nm.
4) The emulsion is dehydrated and dried by a spray drying tower, the air inlet temperature is 105 ℃, the emulsion temperature is 50 ℃, the rotation speed of an atomizer is 10000r/min, and the feeding flow is 20ml/min, so that the aporate dry powder is obtained. Through testing, the content of apoester in the dry powder is 12.0%, the content of all-trans isomer is 96.1%, and the embedding rate is 99.9%. The mixture is preserved for 6 months at 30 ℃ under the condition of 60 percent of humidity, the content of the aporate is 11.9 percent, and the content of all-trans isomer is 95.5 percent.
Example 4
1) 200g of astaxanthin solid with the total trans content of 97.2% is dissolved in 2kg of methyl tertiary butyl ether, the dissolution heating temperature is 90 ℃, and then the astaxanthin solution is pumped into 1.8kg of potassium dihydrogen phosphate aqueous solution with the concentration of 0.1% by using a slurry at the flow rate of 20ml/min, and the astaxanthin solution is stood for 50 minutes at room temperature after the addition of the astaxanthin solution is completed. Then separating the upper methyl tertiary butyl ether phase by centrifugal phase separation to obtain astaxanthin dispersion liquid with the solid content of 10 percent, wherein the astaxanthin crystal grain diameter D90 is less than 200nm.
2) A malic acid-peanut protein complex gel was prepared by the method of example 1.
1kg of the prepared malic acid-peanut protein composite colloid, 50g of sorbitan monooleate and 100g of mannitol are added into 5kg of deionized water at 45 ℃, and the mixture is sheared for 10 minutes by a high-speed shearing machine at 10000r/min to obtain a composite colloid water phase.
3) And mixing the astaxanthin dispersion liquid with the composite colloid water phase, shearing for 25 minutes by a high-speed shearing machine at the shearing speed of 10000r/min to obtain astaxanthin emulsion, carrying out reduced pressure distillation (the pressure is 40 kPa) in the shearing process to remove a small amount of methyl tertiary butyl ether solvent, and finally measuring the emulsion particle diameter D90 of 151nm.
4) The emulsion is dehydrated and dried by a spray drying tower, the air inlet temperature is 120 ℃, the emulsion temperature is 60 ℃, the rotating speed of an atomizer is 9000r/min, and the feeding flow is 30ml/min, so as to obtain astaxanthin dry powder. Through testing, the astaxanthin content in the dry powder is 16.0%, the all-trans isomer content is 97.1%, and the embedding rate is 99.9%. The astaxanthin content is 15.7% and the all-trans isomer content is 96% when stored for 6 months at 30 ℃ under the humidity of 60%.
Comparative example 1
1) 200g of beta-carotene solid with 97% of all-trans content is dissolved in 2kg of ethyl acetate at 80 ℃, then the beta-carotene solution is pumped into 2kg of deionized water by a slurry pump at a flow rate of 10ml/min, and the beta-carotene solution is left to stand for 40 minutes at room temperature after the addition of the beta-carotene solution is completed. Then, the ethyl acetate phase of the upper layer was separated by centrifugal phase separation to obtain a beta-carotene dispersion having a solid content of 5% and a beta-carotene crystal grain diameter D90 of 4.2. Mu.m.
2) Salicylic acid-soy protein complex colloid was prepared according to the method of example 1. 1.5kg of the prepared salicylic acid-soybean protein composite colloid, 40g of ascorbyl palmitate and 400g of glucose are added into 7.5kg of deionized water at 45 ℃, and the mixture is sheared by a high-speed shearing machine for 10 minutes at a shearing speed of 9000r/min, so as to obtain a composite colloid water phase.
3) The beta-carotene dispersion liquid and the composite colloid are mixed, and sheared by a high-speed shearing machine for 30 minutes at the shearing speed of 10000r/min, so as to obtain beta-carotene emulsion, a small amount of ethyl acetate solvent is removed by reduced pressure distillation (the pressure is 50 kPa) in the shearing process, and the final measured emulsion particle diameter D90 is 3.6 mu m.
4) The emulsion is dehydrated and dried by a spray drying tower, the air inlet temperature is 110 ℃, the emulsion temperature is 50 ℃, the rotating speed of an atomizer is 10000r/min, and the feeding flow is 15ml/min, so that the beta-carotene dry powder is obtained. Through testing, the content of beta-carotene in the dry powder is 5.6%, the content of all-trans isomer is 73.1%, and the embedding rate is 82%. The product is preserved for 6 months at 30 ℃ under the condition of 60% humidity, the content of beta-carotene is 3.4%, and the content of all-trans isomer is 45%.
Comparative example 2
1) 200g of beta-carotene solid with 97% of all-trans content is dissolved in 2kg of ethyl acetate, the dissolution temperature is 80 ℃, then the beta-carotene solution is pumped into 2kg of sodium pyrophosphate solution with 0.3wt% of concentration by slurry at the flow rate of 10ml/min, and the beta-carotene solution is stood for 40 minutes at room temperature after the addition of the beta-carotene solution is completed. Then, the ethyl acetate phase at the upper layer was separated by centrifugal phase separation to obtain a beta-carotene dispersion having a solid content of 9% and a beta-carotene crystal grain diameter D90 of 183nm.
2) 1.5kg of soybean protein colloid, 40g of ascorbyl palmitate and 400g of glucose are added into 7.5kg of deionized water at 45 ℃, and the mixture is sheared for 10 minutes by a high-speed shearing machine at the shearing speed of 9000r/min, so as to obtain a soybean protein colloid water phase.
3) The beta-carotene dispersion liquid and the soybean protein colloid are mixed, and sheared by a high-speed shearing machine for 30 minutes, the shearing speed is 10000r/min, the beta-carotene emulsion is obtained, reduced pressure distillation (the pressure is 50 kPa) is carried out in the shearing process, a small amount of ethyl acetate solvent is removed, and finally the emulsion particle diameter D90 measured is 0.9 mu m.
4) The emulsion is dehydrated and dried by a spray drying tower, the air inlet temperature is 110 ℃, the emulsion temperature is 50 ℃, the rotating speed of an atomizer is 10000r/min, and the feeding flow is 15ml/min, so that the beta-carotene dry powder is obtained. Through testing, the content of beta-carotene in the dry powder is 6.7%, the content of all-trans isomer is 90.9%, and the embedding rate is 88%. The product is preserved for 6 months at 30 ℃ and 60% humidity, the content of beta-carotene is 3.2%, and the content of all-trans isomer is 32%.

Claims (14)

1. A preparation method of nanoscale all-trans carotenoid dry powder comprises the following steps:
1) Mixing carotenoid solids with the total trans content of more than 97% with an organic solvent to obtain a carotenoid solution, mixing the carotenoid solution with a phosphate aqueous solution to separate out nanocrystals, and carrying out centrifugal phase separation on the two-phase nanocrystal mixed solution to obtain a carotenoid crystal dispersion liquid with the solid content of 5-20%;
2) Mixing polyphenol-plant protein composite colloid, an emulsifying agent, sugar and warm deionized water, and shearing to obtain a protective colloid water phase mixture;
wherein the polyphenol is one or more of salicylic acid, quinic acid, malic acid, caffeic acid and curcumin, the plant protein is one or more of soybean protein, wheat protein, corn protein and peanut protein, and the preparation method of the polyphenol-plant protein composite colloid comprises the following steps:
dissolving vegetable protein in water to prepare a vegetable protein solution with the concentration of 1-8wt%;
dissolving polyphenol in water to prepare polyphenol solution with the concentration of 0.8-2 wt%;
adjusting the pH of the two solutions to 3.0-7.0 respectively, mixing, and freeze-drying to obtain polyphenol-plant protein composite colloid;
3) Mixing carotenoid crystal dispersion liquid with a protective colloid water phase mixture, and shearing to obtain stably dispersed carotenoid nanoemulsion;
4) And drying the stably dispersed carotenoid nanoemulsion to obtain nanoscale carotenoid dry powder.
2. The method according to claim 1, wherein step 1) the carotenoid is selected from the group consisting of beta-carotene, canthaxanthin, lycopene, astaxanthin, apoester, lutein;
the organic solvent is selected from ethyl formate, ethyl acetate, methyl tertiary butyl ether and isopropyl acetate.
3. The process according to claim 2, wherein in step 1), the mass ratio of the organic solvent to the carotenoid is 10 to 50:1.
4. The method of claim 1, wherein the phosphate of step 1) is one or more of potassium phosphate, potassium pyrophosphate, sodium dihydrogen phosphate, sodium pyrophosphate, calcium pyrophosphate, and potassium dihydrogen phosphate.
5. The method according to claim 4, wherein the concentration of the phosphate aqueous solution is 0.1 to 0.5wt%.
6. The method according to any one of claims 1 to 5, wherein the mass ratio of the phosphate aqueous solution to the carotenoid solution is 0.8 to 4:1.
7. The method of claim 1, wherein the emulsifier of step 2) is one or more of sorbitan monooleate, polyglycerol monooleate, citrate, ascorbyl palmitate.
8. The method according to claim 1 or 7, wherein in the step 2), the mass ratio of the composite colloid to the emulsifier is 20-60:1.
9. The method of claim 1, wherein the sugar of step 2) is one or more of sucrose, glucose, sorbitol, mannitol, fructose.
10. The method according to claim 1 or 9, wherein the mass ratio of complex colloid to sugar is 2-10:1.
11. The method according to claim 1, wherein the temperature of the warm deionized water of step 2) is 30-55 ℃.
12. The method of claim 1 or 11, wherein the mass ratio of deionized water to complex colloid is 4-10:1.
13. The process according to claim 1, wherein the mass ratio of carotenoid crystal dispersion to protective colloid aqueous mixture in step 3) is 0.1-0.4:1.
14. The method according to claim 1, wherein in step 4) spray drying is adopted, the air inlet temperature is 100-120 ℃, the emulsion temperature is 40-70 ℃, the rotating speed of the atomizer is 8000-15000 r/min, and the feeding flow is 10-30 ml/min.
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