CN113575945A - Preparation method of nano-scale high all-trans carotenoid dry powder - Google Patents

Preparation method of nano-scale high all-trans carotenoid dry powder Download PDF

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CN113575945A
CN113575945A CN202110816043.7A CN202110816043A CN113575945A CN 113575945 A CN113575945 A CN 113575945A CN 202110816043 A CN202110816043 A CN 202110816043A CN 113575945 A CN113575945 A CN 113575945A
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carotenoid
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polyphenol
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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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Abstract

The invention provides a preparation method of nanometer grade high 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 a phosphate aqueous solution with the concentration of 0.1-0.5%, and performing centrifugal phase separation to obtain a carotenoid crystal dispersion liquid with the solid content of 5-20%; 2) mixing polyphenol-vegetable protein composite colloid, emulsifier, sugar and water to obtain protective colloid water phase; 3) mixing the carotenoid dispersion with water to obtain an emulsion; 4) and (4) carrying out spray drying on the emulsion to obtain carotenoid dry powder. The invention carries out induced precipitation on the carotenoid by phosphate aqueous solution, and solves the problems of loss of effective components, low content and use of high-toxicity halogenated hydrocarbon solvent in a high-temperature dissolution method; the polyphenol-vegetable protein composite colloid avoids the use of the traditional antioxidant; the obtained dry powder has all-trans content of over 94%, high bioavailability, and high water solubility.

Description

Preparation method of nano-scale high all-trans carotenoid dry powder
Technical Field
The invention relates to a preparation method of nanometer grade high all-trans carotenoid dry powder, belonging to the field of nutritional chemical preparation.
Background
Carotenoids are highly unsaturated compounds having a plurality of conjugated double bonds and methyl branches, and widely occur in nature, and their important representative substances are β -carotene, canthaxanthin, lycopene, astaxanthin, apo ester, lutein, and the like, which have characteristic colors ranging from yellow to red. The substances are widely applied to the industries of food, feed, cosmetics, medicine and the like as nutrients and coloring agents. In addition, part of carotenoid can be used as vitamin A active precursor, and has important physiological function for animals. However, carotenoids are poorly soluble in water and most organic solvents due to their specific chemical structure, and are sensitive to light, temperature, and oxygen, and thus are difficult to be directly applied as products. Therefore, in order to increase the application value of carotenoids in practical production, it is necessary to process carotenoid active ingredients into a preparation product which can be stored for a long time, is prevented from being oxidized, and has a certain bioavailability.
In order to achieve the purpose that the active ingredient of carotenoid is easily absorbed in animal body, the particle size of the active ingredient needs to be reduced, especially when the particle size is reduced to nanometer level, the carotenoid has high bioavailability, and at present, some documents report the preparation method of carotenoid preparation.
European patent No. 0239086 describes a process for the preparation of emulsion formulations of carotenoids by dissolving the carotenoid in an oil and stabilizing the oil phase with a mixture of long chain fatty acid esters with ascorbic acid esters and water soluble starch to give a final product with a carotenoid content of 0.1% to 2%, a very low carotenoid content and a low practical value.
WO/2010/040683 describes a process for the preparation of ready-to-use emulsions by using a glycerol-water mixture as protective colloid, adding modified starch and swelling under heating, then mixing the aqueous phase with a carotenoid oil melt, homogenizing under high speed and high pressure to give a water-dispersible emulsion. The method adopts conventional high temperature melting method, accelerates carotenoid oxidative deterioration process, changes isomer content, and the obtained emulsion product can not be stored for a long time.
Although the preparation process of the carotenoid emulsion preparation is simple, the emulsion preparation has poor product stability and low biological activity in effective components, and finally, the product has low bioavailability and poor applicability. In order to change the stability of carotenoid preparation products, emulsions need to be prepared into stable dry powder products by using different embedding agents.
US5364563 describes a process for the preparation of a powdered formulation of carotenoids by mixing a carotenoid with vegetable oil having a boiling point above 200 ℃ to form a suspension, subjecting the suspension to high temperature dissolution with steam at a temperature up to 200 ℃, mixing the water and oil phases by means of a homogenizer to obtain an emulsion, and spray drying in a fluidized bed loaded with starch to obtain the product. The carotenoid content is greatly lost through such high temperature heating, and the final all-trans content is only 70%. In addition, the use of superheated steam with high temperature and high pressure requires expensive equipment, and the equipment operation requires high requirements, the process is complicated, and the productivity is not high.
US5827539 describes the use of a ball mill to grind an oil dispersion containing carotenoid particles such that the mean diameter of undissolved carotenoid particles in the dispersion is less than 1 micron. The aqueous embedding mixture is formed by dissolving starch as embedding medium, sugar and antioxidant in water. The ground carotenoid-oil dispersion is then emulsified together with the aqueous phase. Finally, the resulting emulsion is dried to produce a powder, which is encapsulated in a protective starch matrix. The high temperature generated by the milling in this process, due to the longer milling time, causes a drastic decrease in the trans-isomer content of the carotenoid and finally results in a carotenoid content of up to 5% being produced by the process. In addition, the method has large energy consumption, and the used equipment is not suitable for large-scale production.
In order to avoid the use of oils or fats as carotenoid solvents, US3998753 describes a process for preparing water-dispersible carotenoid powders wherein the particle size of the carotenoid is less than 1 μm, which comprises (a) dissolving the carotenoid and an antioxidant in a halogenated aliphatic hydrocarbon solvent, said solvent being selected from chloroform, carbon tetrachloride and dichloromethane; (b) forming an aqueous solution of a water-soluble carrier composition of gelatin, a preservative and an emulsifier and adjusting the pH of the solution to 10-11; (c) mixing (a) and (b) under high shear to form an emulsion, and spray drying to obtain carotenoid powder.
In European publication EP0065193 or corresponding US4522743, 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 is as follows: dissolving carotenoid or retinoid in volatile organic solvent at high temperature of about 200 deg.C for less than 10 s. The carotenoid or retinoid is then immediately precipitated in colloidally dispersed form from the resulting molecular dispersion solution by rapid mixing at 50 ℃ with an aqueous solution of a swellable colloid, and the dispersion is finally dried to give a powder preparation.
Both the organic solvent method and the high-temperature dissolution method need high temperature to solve the problem of poor carotenoid solubility, and the high-temperature dissolution process has high requirements on equipment and high energy consumption and does not have industrial advantages. And a large amount of solvent is removed in a protective colloid system, so that the procedure time is long, the carotenoid content and the all-trans isomer content with poor stability are obviously reduced, the particle size is difficult to control at a 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 can keep high content and high all-trans isomer content and have high bioavailability.
The preparation method of the nanometer grade high all-trans carotenoid dry powder provided by the invention comprises the following steps:
1) mixing carotenoid solid with the all-trans content of more than 97% with an organic solvent, dissolving the carotenoid solid in a heating reflux state to obtain a carotenoid solution, slowly dripping the carotenoid solution into a phosphate aqueous solution with a certain concentration to separate out nano crystals with the particle size of 50-300 nm, and finally carrying out centrifugal phase separation on the mixed solution of the two nano crystals to obtain a carotenoid crystal dispersion liquid with the solid content of 5-20%;
2) mixing polyphenol-plant protein composite colloid, emulsifier, 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 aqueous mixture of the protective colloid, shearing for a period of time by a high-speed shearing machine to obtain stably dispersed carotenoid nano emulsion, and removing residual organic solvent in the process; the mass ratio of the carotenoid crystal dispersion liquid to the aqueous mixture of the protective colloid is 0.1-0.4: 1;
4) and (3) carrying out spray drying on the stably dispersed carotenoid nano emulsion, and controlling the air inlet temperature, the emulsion temperature, the atomizer rotating speed and the feeding flow parameters during spraying to obtain the carotenoid dry powder with the content of 5-40%, wherein the content of all-trans carotenoid isomers is more than 94%.
In the method of the present invention, the carotenoid of step 1) is selected from among β -carotene, canthaxanthin, lycopene, astaxanthin, apo ester, lutein, and the like.
In the method of the present invention, the organic solvent in step 1) is selected from one or more of ethyl formate, ethyl acetate, methyl tert-butyl ether and isopropyl acetate.
In the method, in the step 1), the mass ratio of the organic solvent to the carotenoid is 10-50: 1, preferably 10-20: 1; the dissolving temperature is 50-90 ℃, and 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 phosphate aqueous solution is 0.1-0.5 wt%, preferably 0.2-0.3 wt%;
the dripping speed of the 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 method of the present invention, the solid content of the carotenoid crystal dispersion liquid obtained in step 1) is 5 to 20%, preferably 7 to 10%.
In the method of the present invention, the preparation method of the polyphenol-plant protein composite colloid in step 2) comprises:
dissolving plant protein in water to prepare a plant 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;
adjusting the pH of the two solutions to be 3.0-7.0 respectively by using 0.1M HCl and 0.1M NaOH, preferably adjusting the pH of a vegetable protein solution to be 5.5-6.0, preferably adjusting the pH of a polyphenol solution to be 5.0-5.5, then dropwise adding the polyphenol solution into the vegetable protein solution under magnetic stirring or dropwise adding the vegetable protein solution into the polyphenol solution, wherein the stirring speed is 300-600 rpm, the mixing temperature is 30-40 ℃, and then performing a freeze drying process to obtain the polyphenol-vegetable protein composite colloid.
The polyphenol is one or more of salicylic acid, quinic acid, malic acid, caffeic acid, and curcumin. The polyphenol-vegetable 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 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, the sugar in the step 2) is one or more of sucrose, glucose, sorbitol, mannitol and fructose; the mass ratio of the composite colloid to the sugar is 2-10: 1, preferably 4-8: 1.
In the method, the temperature of the warm deionized water in the step 2) is 30-55 ℃, and preferably 45 ℃; the mass ratio of the deionized water to the composite colloid is 4-10: 1, preferably 5-8: 1.
In the method, 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 5-20 min, preferably 10-15 min.
In the method, 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 15-40 min, preferably 25-30 min.
In the method of the present invention, the method for removing the residual organic solvent in step 3) is atmospheric distillation, and if appropriate, reduced pressure distillation may be adopted, and the distillation pressure is 40 to 80kPa, preferably 50 to 60 kPa.
In the method, the air inlet temperature in the step 4) is 100-120 ℃, and preferably 110-115 ℃; the temperature of the emulsion is 40-70 ℃, preferably 50-55 ℃; the rotating speed of the atomizer is 8000-15000 r/min, preferably 10000-12000 r/min; the feeding flow rate is 10-30 ml/min, preferably 15-20 ml/min.
The core of the invention is that the carotenoid solid is pretreated by adopting an induced precipitation method to obtain the nano carotenoid dispersion liquid at the nano level, and the phosphate aqueous solution promotes the precipitation of nano crystals, so that the preparation of the nano emulsion is more convenient and quicker, the problems of loss of effective components and low content of a high-temperature dissolution method are solved, meanwhile, the carotenoid is prevented from being oxidized and the use of high-toxicity halogenated hydrocarbon is avoided, and the industrial production is more facilitated. In addition, the polyphenol-vegetable protein composite colloid is used as a protective colloid, and due to the oxidation resistance of polyphenol and the emulsifying property of the composite colloid, the use of a traditional antioxidant is avoided, so that the stability of the product is more excellent, 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 carotenoid crystal grain diameter D90 is less than 200nm, and the all-trans carotenoid isomer content is more than 94%.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
1) 200g of beta-carotene solid with the all-trans content of 97 percent is dissolved in 2kg of ethyl acetate at the dissolving temperature of 80 ℃, then the beta-carotene solution is pumped into 2kg of sodium pyrophosphate aqueous solution with the concentration of 0.3 percent by weight by a slurry pump at the flow rate of 10ml/min, and the beta-carotene solution is kept stand for 40 minutes at room temperature after the addition of the beta-carotene solution is finished. Then separating the upper ethyl acetate phase by centrifugal phase separation to obtain beta-carotene dispersion liquid with solid content of 9%, wherein the grain diameter D90 of beta-carotene crystal is less than 200 nm.
2) The preparation process of the salicylic acid-soybean protein composite colloid comprises the following steps: dissolving 1kg of soy protein in 50kg of deionized water, and adjusting the pH to 5.5 by using 0.1M HCl solution; dissolving salicylic acid 0.5kg in deionized water 50kg, and adjusting pH to 5.0 with 0.1M NaOH solution; then under the magnetic stirring, the rotating 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 by 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 for 10 minutes by a high-speed shearing machine at the shearing speed of 9000r/min to obtain a composite colloid water phase.
4) Mixing the beta-carotene dispersion liquid and the composite colloid water, shearing for 30 minutes by a high-speed shearing machine at the shearing speed of 10000r/min to obtain beta-carotene emulsion, and distilling under reduced pressure (the pressure is 50kPa) to remove a small amount of ethyl acetate solvent in the shearing process, wherein the finally measured particle size D90 of the emulsion is 176 nm.
5) And (3) dehydrating and drying the emulsion in a spray drying tower at the air inlet temperature of 110 ℃, the emulsion temperature of 50 ℃, the rotation speed of an atomizer of 10000r/min and the feeding flow of 15ml/min to obtain the beta-carotene dry powder. Tests show that the content of beta-carotene in the dry powder is 9.1%, the content of all-trans isomers is 94.5%, and the embedding rate is 99.8%. The product is stored at 30 deg.C and humidity of 60% for 6 months, and has beta-carotene content of 9.0% and all-trans isomer content of 94.4%.
Example 2
1) 200g of a canthaxanthin solid having an all-trans content of 97.3% was dissolved in 2.1kg of ethyl formate at a dissolution temperature of 60 ℃ and then the canthaxanthin solution was pumped into 2.4kg of a 0.32 wt% potassium phosphate aqueous solution at a flow rate of 12ml/min by a slurry pump, and after the addition of the canthaxanthin solution was completed, the mixture was allowed to stand at room temperature for 30 minutes. Then separating the upper ethyl formate phase by centrifugal phase separation to obtain the canthaxanthin dispersion liquid with the solid content of 8 percent, wherein the particle size of the canthaxanthin crystal D90 is less than 200 nm.
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 citrate and 385g of cane sugar are added into 7kg of deionized water with the temperature of 45 ℃, and the mixture is sheared for 15 minutes by a high-speed shearing machine, wherein the shearing rotating speed is 11000r/min, so as to obtain a composite colloid water phase.
3) Mixing the canthaxanthin dispersion liquid and the composite colloidal water, shearing by a high-speed shearing machine for 30 minutes at the shearing speed of 10000r/min to obtain a canthaxanthin emulsion, and performing reduced pressure distillation (the pressure is 65kPa) in the shearing process to remove a small amount of ethyl formate solvent, wherein the finally measured particle size D90 of the emulsion is 186 nm.
4) And (3) dehydrating and drying the emulsion in a spray drying tower at the air inlet temperature of 120 ℃, the emulsion temperature of 60 ℃, the atomizer rotating speed of 10000r/min and the feeding flow of 20ml/min to obtain canthaxanthin dry powder. Through tests, 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 product is stored at 30 deg.C and humidity of 60% for 6 months, and has canthaxanthin content of 10.1% and all-trans isomer content of 95.0%.
Example 3
1) 200g of apo ester solid with the all-trans content of 98.0 percent is dissolved in 2.9kg of isopropyl acetate at the dissolving temperature of 85 ℃, then the apo ester solution is pumped into 2.8kg of potassium pyrophosphate aqueous solution with the concentration of 0.28 percent by a slurry pump at the flow rate of 16ml/min, and the apo ester solution is stood for 30 minutes at room temperature after the addition of the apo ester solution is finished. And then, carrying out centrifugal phase separation to separate the isopropyl acetate at the upper layer to obtain the apoester dispersion liquid with the solid content of 7 percent, wherein the particle size D90 of the apoester crystal is less than 200 nm.
2) A curcumin-wheat protein complex colloid was prepared according to the method of example 1.
Adding 1.03kg of the prepared curcumin-wheat protein composite colloid, 30g of polyglycerol monooleate and 370g of fructose into 8kg of deionized water at 45 ℃, and shearing for 20 minutes by a high-speed shearing machine at the shearing speed of 10000r/min to obtain a composite colloid water phase.
3) Mixing the apoester dispersion liquid and the composite colloid water phase, shearing for 25 minutes by a high-speed shearing machine at the shearing speed of 10000r/min to obtain apoester emulsion, and performing reduced pressure distillation (the pressure is 65kPa) to remove a small amount of isopropyl acetate solvent in the shearing process, wherein the finally measured particle diameter D90 of the emulsion is 195 nm.
4) And (3) dehydrating and drying the emulsion in a spray drying tower at the air inlet temperature of 105 ℃, the emulsion temperature of 50 ℃, the rotation speed of an atomizer of 10000r/min and the feeding flow of 20ml/min to obtain the aporate dry powder. Tests show that the content of the apo-ester in the dry powder is 12.0 percent, the content of the all-trans isomer is 96.1 percent, and the embedding rate is 99.9 percent. The product is stored at 30 deg.C and humidity of 60% for 6 months, and has apo ester content of 11.9% and all-trans isomer content of 95.5%.
Example 4
1) 200g of an astaxanthin solid having an all-trans content of 97.2% was dissolved in 2kg of methyl t-butyl ether at a heating temperature of 90 ℃ and then the astaxanthin solution was pumped into 1.8kg of an aqueous solution containing potassium dihydrogen phosphate having a concentration of 0.1% at a flow rate of 20ml/min by a slurry pump and allowed to stand at room temperature for 50 minutes after the addition of the astaxanthin solution was completed. And then separating the upper layer of methyl tert-butyl ether phase by centrifugal phase separation to obtain an astaxanthin dispersion liquid with the solid content of 10%, wherein the particle size D90 of the astaxanthin crystal is less than 200 nm.
2) A malic acid-peanut protein complex colloid was prepared according to 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 the shearing speed of 10000r/min to obtain a composite colloid water phase.
3) Mixing the astaxanthin dispersion liquid and the composite colloid water, shearing for 25 minutes by a high-speed shearing machine at the shearing speed of 10000r/min to obtain an astaxanthin emulsion, and distilling under reduced pressure (the pressure is 40kPa) to remove a small amount of methyl tert-butyl ether solvent in the shearing process, wherein the finally measured particle size D90 of the emulsion is 151 nm.
4) And (3) dewatering and drying the emulsion by a spray drying tower, wherein 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 to obtain astaxanthin dry powder. Through tests, 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%. Storing at 30 deg.C and humidity of 60% for 6 months, wherein astaxanthin content is 15.7%, and all-trans isomer content is 96%.
Comparative example 1
1) 200g of beta-carotene solid with the all-trans content of 97 percent is dissolved in 2kg of ethyl acetate at the dissolving temperature of 80 ℃, then the beta-carotene solution is pumped into 2kg of deionized water by a slurry pump at the flow rate of 10ml/min, and the mixture is kept stand at room temperature for 40 minutes after the beta-carotene solution is added. Then, the upper layer of ethyl acetate phase was separated by centrifugal phase separation to obtain a dispersion of beta-carotene having a solid content of 5% and a crystal particle diameter D90 of 4.2 μm.
2) A 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 for 10 minutes by a high-speed shearing machine at the shearing speed of 9000r/min to obtain a composite colloid water phase.
3) Mixing the beta-carotene dispersion liquid and the composite colloid water, shearing for 30 minutes by a high-speed shearing machine at the shearing speed of 10000r/min to obtain beta-carotene emulsion, and distilling under reduced pressure (the pressure is 50kPa) to remove a small amount of ethyl acetate solvent in the shearing process, wherein the finally measured particle diameter D90 of the emulsion is 3.6 mu m.
4) And (3) dehydrating and drying the emulsion in a spray drying tower at the air inlet temperature of 110 ℃, the emulsion temperature of 50 ℃, the rotation speed of an atomizer of 10000r/min and the feeding flow of 15ml/min to obtain the beta-carotene dry powder. Tests show that 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 stored at 30 deg.C and humidity of 60% for 6 months, and has beta-carotene content of 3.4% and all-trans isomer content of 45%.
Comparative example 2
1) 200g of beta-carotene solid with the all-trans content of 97 percent is dissolved in 2kg of ethyl acetate at the dissolving temperature of 80 ℃, then the beta-carotene solution is pumped into 2kg of sodium pyrophosphate solution with the concentration of 0.3 percent by weight by a slurry pump at the flow rate of 10ml/min, and the beta-carotene solution is kept stand for 40 minutes at room temperature after the addition of the beta-carotene solution is finished. Then, the upper layer of ethyl acetate phase was separated by centrifugal phase separation to obtain a dispersion of beta-carotene having a solid content of 9% and a particle diameter D90 of the beta-carotene crystal of 183 nm.
2) 1.5kg of soybean protein colloid, 40g of ascorbyl palmitate and 400g of glucose are added into 7.5kg of deionized water with the temperature of 45 ℃, and the mixture is sheared for 10 minutes by a high-speed shearing machine, wherein the shearing rotating speed is 9000r/min, so that a soybean protein colloid water phase is obtained.
3) Mixing the beta-carotene dispersion liquid and the soybean protein 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, and distilling under reduced pressure (the pressure is 50kPa) to remove a small amount of ethyl acetate solvent in the shearing process, wherein the finally measured particle size D90 of the emulsion is 0.9 mu m.
4) And (3) dehydrating and drying the emulsion in a spray drying tower at the air inlet temperature of 110 ℃, the emulsion temperature of 50 ℃, the rotation speed of an atomizer of 10000r/min and the feeding flow of 15ml/min to obtain the beta-carotene dry powder. Through tests, 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 stored at 30 deg.C and humidity of 60% for 6 months, and has beta-carotene content of 3.2% and all-trans isomer content of 32%.

Claims (10)

1. A preparation method of nanometer grade high all-trans carotenoid dry powder comprises the following steps:
1) mixing a carotenoid solid with an all-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 precipitate a nanocrystal, and carrying out centrifugal phase separation on the two-phase nanocrystal mixed solution to obtain a carotenoid crystal dispersion liquid with a solid content of 5-20%;
2) mixing polyphenol-vegetable protein composite colloid, emulsifier, sugar and warm deionized water, and shearing to obtain a protective colloid water-phase mixture;
3) mixing the carotenoid crystal dispersion liquid with the aqueous mixture of the protective colloid and shearing to obtain stably dispersed carotenoid nano emulsion;
4) and drying the stably dispersed carotenoid nano emulsion to obtain the nano carotenoid dry powder.
2. The method according to claim 1, wherein the carotenoid of step 1) is selected from the group consisting of β -carotene, canthaxanthin, lycopene, astaxanthin, apoester, lutein;
the organic solvent is selected from ethyl formate, ethyl acetate, methyl tert-butyl ether and isopropyl acetate; preferably, the mass ratio of the organic solvent to the carotenoid is 10-50: 1.
3. The method according to claim 1 or 2, wherein the phosphate of step 1) is one or more of potassium phosphate, potassium pyrophosphate, sodium dihydrogen phosphate, sodium pyrophosphate, calcium pyrophosphate, potassium dihydrogen phosphate;
preferably, the concentration of the phosphate aqueous solution is 0.1-0.5 wt%;
preferably, the mass ratio of the phosphate aqueous solution to the carotenoid solution is 0.8-4: 1.
4. The method according to any one of claims 1 to 3, wherein the polyphenol of step 2) is one or more of salicylic acid, quinic acid, malic acid, caffeic acid, curcumin, and the plant protein is one or more of soy protein, wheat protein, corn protein, and peanut protein.
5. The method according to any one of claims 1 to 4, wherein the polyphenol-plant protein complex colloid of step 2) is prepared by:
dissolving plant protein in water to prepare a plant protein solution with the concentration of 1-8 wt%;
dissolving polyphenol in water to prepare polyphenol solution with the concentration of 0.8-2 wt%;
and adjusting the pH values of the two solutions to be 3.0-7.0 respectively, then mixing, and freeze-drying to obtain the polyphenol-vegetable protein composite colloid.
6. The method according to any one of claims 1 to 5, wherein the emulsifier of step 2) is one or more of sorbitan monooleate, polyglycerol monooleate, citric acid ester, ascorbyl palmitate;
preferably, the mass ratio of the composite colloid to the emulsifier is 20-60: 1.
7. The method according to any one of claims 1 to 6, wherein the sugar of step 2) is one or more of sucrose, glucose, sorbitol, mannitol, fructose;
preferably, the mass ratio of the composite colloid to the sugar is 2-10: 1.
8. The method according to any one of claims 1 to 7, wherein the temperature of the warm deionized water in the step 2) is 30 to 55 ℃;
preferably, the mass ratio of the deionized water to the composite colloid is 4-10: 1.
9. The method according to any one of claims 1 to 8, wherein the mass ratio of the carotenoid crystal dispersion liquid in step 3) to the aqueous mixture of protective colloids is 0.1 to 0.4: 1.
10. The method according to any one of claims 1 to 9, wherein the spray drying is adopted in the step 4), the inlet air temperature is 100-120 ℃, the emulsion temperature is 40-70 ℃, the rotation speed of the atomizer is 8000-15000 r/min, and the feeding flow rate is 10-30 ml/min.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115153018A (en) * 2022-07-04 2022-10-11 新昌新和成维生素有限公司 Production method and production system of carotenoid emulsion
CN115772109A (en) * 2022-12-06 2023-03-10 万华化学集团股份有限公司 Preparation method of canthaxanthin crystal

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1362406A (en) * 2000-12-21 2002-08-07 Basf公司 Method for producing one or more kinds of oxydic carotenoid dry powder
CN1374035A (en) * 2001-01-31 2002-10-16 巴斯福股份公司 Process for producing one or more kinds of dry powder of carotenoid
CN1942106A (en) * 2004-02-06 2007-04-04 巴斯福股份公司 Method for producing dry powders of one or several carotenoids
CN101873804A (en) * 2007-11-29 2010-10-27 巴斯夫欧洲公司 Pulverulent carotenoid preparation for colouring drinks
JP2016159206A (en) * 2015-02-27 2016-09-05 ユーハ味覚糖株式会社 Method for producing nanoparticle having improved physiologically active substance carrying capacity
CN105996038A (en) * 2016-07-05 2016-10-12 南昌大学 Method for preparing high-stability nano emulsion with controllable nutrient release
CN111296730A (en) * 2020-03-06 2020-06-19 广州市食品工业研究所有限公司 Lutein nanoemulsion with good stability and preparation method thereof
CN111419821A (en) * 2020-04-17 2020-07-17 万华化学集团股份有限公司 Preparation method of high all-trans carotenoid microcapsules
CN111903846A (en) * 2020-07-31 2020-11-10 浙江新和成股份有限公司 Stable carotenoid microcapsule with high bioavailability and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1362406A (en) * 2000-12-21 2002-08-07 Basf公司 Method for producing one or more kinds of oxydic carotenoid dry powder
CN1374035A (en) * 2001-01-31 2002-10-16 巴斯福股份公司 Process for producing one or more kinds of dry powder of carotenoid
CN1942106A (en) * 2004-02-06 2007-04-04 巴斯福股份公司 Method for producing dry powders of one or several carotenoids
CN101873804A (en) * 2007-11-29 2010-10-27 巴斯夫欧洲公司 Pulverulent carotenoid preparation for colouring drinks
JP2016159206A (en) * 2015-02-27 2016-09-05 ユーハ味覚糖株式会社 Method for producing nanoparticle having improved physiologically active substance carrying capacity
CN105996038A (en) * 2016-07-05 2016-10-12 南昌大学 Method for preparing high-stability nano emulsion with controllable nutrient release
CN111296730A (en) * 2020-03-06 2020-06-19 广州市食品工业研究所有限公司 Lutein nanoemulsion with good stability and preparation method thereof
CN111419821A (en) * 2020-04-17 2020-07-17 万华化学集团股份有限公司 Preparation method of high all-trans carotenoid microcapsules
CN111903846A (en) * 2020-07-31 2020-11-10 浙江新和成股份有限公司 Stable carotenoid microcapsule with high bioavailability and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115153018A (en) * 2022-07-04 2022-10-11 新昌新和成维生素有限公司 Production method and production system of carotenoid emulsion
CN115153018B (en) * 2022-07-04 2023-07-21 新昌新和成维生素有限公司 Production method and production system of carotenoid emulsion
CN115772109A (en) * 2022-12-06 2023-03-10 万华化学集团股份有限公司 Preparation method of canthaxanthin crystal

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