A process for the preparation of a high bioavailability yellow series beta-carotene powder
By using lipase to convert β-carotene into its cis isomer and combining this with instantaneous heating and high-pressure homogenization techniques, the solubility and bioactivity issues in the preparation of β-carotene oil phase were solved, resulting in a highly bioavailable yellow β-carotene powder suitable for functional beverages and nutrient solutions.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WANHUA CHEM GRP CO LTD
- Filing Date
- 2022-12-08
- Publication Date
- 2026-05-19
AI Technical Summary
Existing technologies struggle to avoid residual organic solvents, maintain fineness and bioactivity when preparing β-carotene oil phases, especially given the issues of easy degradation and isomerization at high temperatures.
Lipase was used to induce the conversion of β-carotene to its cis isomer. Combined with instantaneous heating and high-pressure homogenization, a yellow β-carotene powder with high bioavailability was prepared. The stability of the isomer conversion and the stability of the emulsion were ensured by the synergistic effect of oil phase antioxidants and stabilizers.
It improves the solubility and bioactivity of β-carotene, avoids high-temperature degradation, and produces an emulsion with a particle size of less than 0.3 μm. The all-trans isomer accounts for more than 70% of the product, making it suitable for functional beverages and nutritional solutions.
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Figure BDA0003987786040000031 
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Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing carotenoid powder, and more particularly to a method for preparing a high-bioavailability yellow β-carotene powder. Background Technology
[0002] Carotenoids are a class of polyene compounds with multiple unsaturated bonds. They can be used as functional health ingredients or colorants in food, such as α-carotene, β-carotene, 8'-apo-β-carotenal, ethyl 8'-apo-β-carotene, canthaxanthin, astaxanthin, lycopene, lutein, zeaxanthin, or crocin.
[0003] The preparation process of carotenoid microcapsule formulations generally involves several steps: first, dissolving water-soluble colloids in water to obtain an aqueous phase; second, dissolving, melting, or dispersing carotenoid crystals and antioxidants through some means to form an oil phase; and third, thoroughly mixing the aqueous and oil phases to form an oil-in-water dispersion emulsion. Depending on the needs, this dispersion emulsion can be granulated to obtain carotenoid microcapsule powder or microparticles. Among these steps, the preparation of the oil phase is the most challenging, mainly because carotenoid crystals have poor solubility, high melting points, and are prone to degradation and isomerization at high temperatures.
[0004] Currently, there are three conventional methods for preparing the β-carotene oil phase: one is to dissolve β-carotene in an organic solvent to form an oil phase, then mix and emulsify it with an aqueous phase, and finally remove the organic solvent, as disclosed in patent US20100267838A1. The disadvantage of this method is that it requires a large amount of organic solvent, and it is impossible to completely remove the organic solvent, especially in emulsions where the presence of emulsifiers makes complete removal even more difficult. These solvents pose a potential hazard during the formulation process and may remain in the final product.
[0005] The second method involves mixing β-carotene crystals with vegetable oil and then grinding them. The advantage of this method is that no organic solvents are used in the process, eliminating safety concerns. Furthermore, the carotenoid molecules are not subjected to high temperatures, resulting in a high all-trans content. However, a significant drawback is that conventional methods often fail to grind carotenoid crystals to a sufficiently fine degree, leading to low bioavailability in the final product. For example, patent WO1991006292A1 requires the addition of large amounts of alcohol solvents such as glycerol and propylene glycol to the formulation to reduce the viscosity of the oil phase during grinding in order to grind β-carotene to the appropriate fineness. This is detrimental to increasing the content of the active ingredient in the final product and its stability.
[0006] Third, carotenoid crystals are dissolved at a high temperature of around 180°C to obtain an oil phase, such as the method used in patent US20110207831A1. A significant drawback of this method is that at such a high temperature, a large portion of the carotenoid molecules will degrade or undergo isomerization from all-trans to cis, greatly reducing their biological activity. Moreover, the color of the final carotenoid solution will change, making it unsuitable for use in yellow-toned nutrients and beverages.
[0007] Based on the current state of the technology, it is necessary to find a simple and efficient method to prepare yellow β-carotene powder that can change the form of β-carotene to amorphous while ensuring the highest possible bioactivity. Summary of the Invention
[0008] To address the aforementioned technical problems, this invention proposes a method for preparing a high-bioavailability yellow β-carotene powder. This invention utilizes lipase to induce partial decomposition of oils into fatty acids. Undissolved β-carotene is converted to its cis isomer under the action of fatty acids. The cis isomer has higher solubility than the all-trans isomer, thus enhancing the solubility of β-carotene in the oil phase. Furthermore, during the emulsification process, this invention heats the aqueous phase using a short-term heating method. The short heating time avoids the degradation and isomerization of the all-trans isomer. Simultaneously, the processing temperature of 40-120℃ promotes the conversion of the cis isomer to the all-trans isomer, ensuring a high proportion of all-trans isomers, thereby improving the product's bioactivity. Moreover, the β-carotene powder obtained by this method is yellow, making it widely applicable in functional beverages and nutritional solutions.
[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0010] A method for preparing a high-bioavailability yellow β-carotene powder includes the following steps:
[0011] 1) Preparation of oil phase
[0012] β-carotene, oil phase antioxidants, stabilizers, oils, and lipases are mixed and dispersed by stirring at 30-60°C, preferably 40-50°C, to obtain the oil phase;
[0013] 2) Preparation of aqueous phase
[0014] Water-soluble colloids, sugar fillers, aqueous antioxidants, and acidity regulators are added to pure water and stirred at 30-100°C, preferably 50-60°C, to dissolve and obtain an aqueous phase.
[0015] 3) Emulsification
[0016] The oil phase is instantaneously heated to 40-120℃, preferably 60-100℃, and added dropwise to the aqueous phase. The primary emulsion is obtained by high-speed shearing, and the final emulsion is obtained by high-pressure homogenization.
[0017] Preferably, the instantaneous heating operation time is 5-50 seconds, more preferably 10-30 seconds;
[0018] 4) Spray drying
[0019] The final emulsion was spray-dried to obtain β-carotene powder.
[0020] As a preferred embodiment, in steps 1) and 2), the percentages of each raw material are as follows, based on the total mass of the raw materials as 100%:
[0021]
[0022] Preferably, the amount of pure water used in step 2) is 1-2 times the total mass of the above raw materials.
[0023] As a preferred embodiment, the oil phase antioxidant is one or more of butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), tert-butylhydroquinone (TBHQ), tocopherol, and vitamin C palmitate.
[0024] As a preferred embodiment, the stabilizer is one or more of zinc laurate, zinc caprylate, and zinc benzoate.
[0025] As a preferred embodiment, the oil is one or more of corn oil, soybean oil, sunflower seed oil, rapeseed oil, and caprylic / capric triglycerides.
[0026] As a preferred embodiment, the water-soluble colloid is one or more of gelatin, sodium lignosulfonate, calcium lignosulfonate, sodium octenyl succinate starch, and gum arabic.
[0027] As a preferred embodiment, the sugar filler is one or more of sucrose, glucose, glucose syrup, maltodextrin, fructose, thiodextrin, and maltodextrin.
[0028] As a preferred embodiment, the aqueous antioxidant is one or more of ascorbic acid, sodium ascorbate, and isoascorbic acid.
[0029] As a preferred embodiment, the acidity regulator is one or more of sodium citrate, potassium citrate, sodium lactate, sodium acetate, and potassium acetate; preferably sodium citrate and / or sodium lactate.
[0030] Preferably, in step 2), the pH of the aqueous phase is adjusted to 4.5-6 using an acidity regulator.
[0031] As a preferred embodiment, the high-speed shearing conditions in step 3) are: rotation speed 3000-8000 rpm, time 10-30 min;
[0032] Preferably, the gauge pressure of the high-pressure homogenizer in step 3) is 30-100 MPa, more preferably 50-60 MPa.
[0033] Preferably, in step 4), during the spray drying process, the inlet air temperature is 150-200℃, the outlet air temperature is 80-100℃, and the atomizer speed is 100-120HZ.
[0034] The above preparation method provided by the present invention can produce β-carotene emulsion with a particle size of <0.3μm and β-carotene powder with an all-trans isomer content of >70%.
[0035] The beneficial effects of this invention are as follows:
[0036] (1) By adding lipase to the β-carotene oil phase, the all-trans isomer is first converted into the cis isomer with higher solubility, thereby increasing the solubility of β-carotene. Then, by treating at a lower temperature, the cis isomer is converted into the all-trans isomer, thereby increasing the proportion of all-trans isomers in the product and improving the bioavailability of the product.
[0037] (2) It can make the β-carotene oil phase enter the aqueous phase emulsification under lower temperature conditions, avoid the loss of all-trans isomers caused by traditional high temperature process, and obtain yellow β-carotene powder.
[0038] (3) By synergistically adjusting the oil phase formulation with oil phase antioxidants and stabilizers, the transformation of cis-trans isomers is ensured to proceed stably, and the resulting emulsion has good stability. Detailed Implementation
[0039] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.
[0040] I. Source of main raw materials in the example:
[0041] β-Carotene: Provided according to the method in Example 1 of patent CN108752251A;
[0042] Lipase: Zhengzhou Kangyuan Chemical Products Co., Ltd.;
[0043] All other reagents are general-purpose, commercially available, chemically pure reagents.
[0044] II. Main Analytical Methods and Instruments:
[0045] Liquid chromatography characterization: Agilent 1260 liquid chromatograph, Sphersorb C18 column. The UV-Vis spectrophotometer was a Hitachi L7420, the chromatography workstation data processing system was a ChomatoPdc C-RIA, and the stationary phase was Zorbax-SIL. Chromatographic conditions: mobile phase was a methanol / acetonitrile mixture of 9 / 1 (v / v), detection temperature was 40℃, flow rate was 1 mL / min, and wavelength was 455 nm. Qualitative and quantitative analysis of the product composition was performed.
[0046] Homogenizer: GEA, Germany;
[0047] Spray drying tower: Wuxi Modern Drying Equipment Co., Ltd.;
[0048] Laser particle tester: Saisway Technology Co., Ltd.
[0049] Example 1
[0050] 1) Mix 1.2 kg β-carotene, 2 kg tocopherol, 0.2 kg zinc caprylate, 8 kg caprylate glycerol, and 0.05 kg lipase, and stir and disperse at 40℃ and 3000 rpm for 10 min;
[0051] 2) Add 40kg of sodium octenyl succinate starch, 42kg of maltodextrin, 3kg of sodium ascorbate, and 0.5kg of sodium citrate to 96.9kg of pure water and stir at 60℃ and 3000rpm for 20min to dissolve.
[0052] 3) The oil phase in step 1) was instantly heated to 80°C within 20 seconds and then dropped into the aqueous phase. The primary emulsion was obtained by high-speed shearing at 8000 rpm for 20 minutes. The final emulsion was obtained by high-pressure homogenization at 50 MPa for 5 minutes. The particle size of the emulsion was tested as shown in Table 1.
[0053] 4) The above final emulsion is spray-dried in a spray drying tower with an inlet air temperature of 180°C, an outlet air temperature of 90°C, and an atomizer speed of 100Hz to obtain β-carotene powder.
[0054] Example 2
[0055] 1) Mix 1.2 kg β-carotene, 5 kg ascorbyl palmitate, 0.1 kg zinc laurate, 5 kg rapeseed oil, and 0.1 kg lipase, and stir and disperse at 50℃ and 3000 rpm for 10 min;
[0056] 2) Add 30kg gum arabic, 55kg sucrose, 2kg ascorbic acid, and 0.5kg potassium citrate to 98.8kg pure water and stir at 50℃ and 3000rpm for 20min to dissolve.
[0057] 3) The oil phase in step 1) was instantly heated to 100°C within 15 seconds and then added dropwise to the aqueous phase. The primary emulsion was obtained by high-speed shearing at 5000 rpm for 20 minutes. The final emulsion was obtained by high-pressure homogenization at 60 MPa for 5 minutes. The particle size of the emulsion was tested as shown in Table 1.
[0058] 4) The above final emulsion is spray-dried in a spray drying tower with an inlet air temperature of 150°C, an outlet air temperature of 80°C, and an atomizer speed of 120 Hz to obtain β-carotene powder.
[0059] Example 3
[0060] 1) Mix 1.2 kg β-carotene, 3 kg butylated hydroxytoluene, 0.15 kg zinc benzoate, 10 kg corn oil, and 0.01 kg lipase, and stir and disperse at 50℃ and 3000 rpm for 10 min;
[0061] 2) Add 50kg sodium lignosulfonate, 30kg glucose, 5kg isoascorbic acid and 0.1kg sodium lactate to 98.8kg pure water and stir at 40℃ and 3000rpm for 20min to dissolve.
[0062] 3) The oil phase in step 1) was instantly heated to 60°C within 30 seconds and then added dropwise to the aqueous phase. The primary emulsion was obtained by high-speed shearing at 3000 rpm for 20 minutes. The final emulsion was obtained by high-pressure homogenization at 100 MPa for 5 minutes. The particle size of the emulsion was tested as shown in Table 1.
[0063] 4) The above final emulsion is spray-dried in a spray drying tower with an inlet air temperature of 200℃, an outlet air temperature of 90℃, and an atomizer speed of 100Hz to obtain β-carotene powder.
[0064] Example 4
[0065] 1) Mix 5.2 kg of β-carotene, 4 kg of butylated hydroxyanisole, 0.5 kg of zinc laurate, 7 kg of sunflower seed oil, and 0.1 kg of lipase, and stir and disperse at 50℃ and 3000 rpm for 10 min;
[0066] 2) Add 60kg of calcium lignosulfonate, 20kg of fructose, 3kg of ascorbic acid, and 0.6kg of sodium acetate to 98.8kg of pure water and stir at 50℃ and 3000rpm for 20min to dissolve.
[0067] 3) The oil phase in step 1) was instantly heated to 80°C within 20 seconds and then dropped into the aqueous phase. The primary emulsion was obtained by high-speed shearing at 8000 rpm for 20 minutes. The final emulsion was obtained by high-pressure homogenization at 30 MPa for 5 minutes. The particle size of the emulsion was tested as shown in Table 1.
[0068] 4) The above final emulsion is spray-dried in a spray drying tower with an inlet air temperature of 180°C, an outlet air temperature of 90°C, and an atomizer speed of 100Hz to obtain β-carotene powder.
[0069] Example 5
[0070] 1) Mix 0.12 kg β-carotene, 1 kg tert-butylhydroquinone, 0.1 kg zinc laurate, 10 kg soybean oil, and 0.05 kg lipase, and stir and disperse at 50℃ and 3000 rpm for 10 min;
[0071] 2) Add 10kg gelatin, 70kg oligomaltose, 8kg ascorbic acid, and 0.5kg potassium acetate to 99.8kg pure water and stir at 50℃ and 3000rpm for 20min to dissolve.
[0072] 3) The oil phase in step 1) was instantly heated to 80°C within 20 seconds and then added dropwise to the aqueous phase. The primary emulsion was obtained by high-speed shearing at 5000 rpm for 20 minutes. The final emulsion was obtained by high-pressure homogenization at 60 MPa for 5 minutes. The particle size of the emulsion was tested as shown in Table 1.
[0073] 4) The above final emulsion is spray-dried in a spray drying tower with an inlet air temperature of 180°C, an outlet air temperature of 90°C, and an atomizer speed of 100Hz to obtain β-carotene powder.
[0074] Comparative Example 1
[0075] β-carotene powder was prepared using essentially the same method as in Example 1, except that lipase was not added during the preparation of the oil phase in step 1).
[0076] Comparative Example 2
[0077] β-carotene powder was prepared using a method essentially the same as in Example 1, except that in step 3), the oil phase was subjected to an instantaneous high-temperature treatment at 180°C for 20 seconds when preparing the emulsion.
[0078] Comparative Example 3
[0079] β-carotene powder was prepared using a method essentially the same as in Example 1, except that in step 1), tocopherol and zinc caprylate were not added during the preparation of the oil phase.
[0080] The β-carotene powders prepared in each embodiment and comparative example were tested for the initial particle size of the emulsion (denoted as particle size A), the particle size after the emulsion was stored for 24 hours (denoted as particle size B), the powder color, the β-carotene content in the powder (denoted as β-carotene content A), the β-carotene content after 12 months of storage (denoted as β-carotene content B), the initial all-trans percentage (denoted as all-trans percentage A), and the all-trans percentage after 12 months of storage (denoted as all-trans percentage B). The test results are shown in Table 1.
[0081] Table 1. Product Test Results
[0082]
[0083] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.
Claims
1. A method for preparing a high-bioavailability yellow β-carotene powder, characterized in that, Includes the following steps: 1) Preparation of oil phase β-carotene, oil phase antioxidants, stabilizers, oils and lipases are mixed and dispersed by stirring at 40-50℃ to obtain the oil phase; 2) Preparation of aqueous phase Water-soluble colloids, sugar fillers, aqueous antioxidants, and acidity regulators are added to pure water and stirred at 40-60°C to dissolve, thus obtaining the aqueous phase. 3) Emulsification The oil phase is instantaneously heated to 60-100℃ and added dropwise to the aqueous phase. The primary emulsion is obtained by high-speed shearing, and the final emulsion is obtained by high-pressure homogenization. The instantaneous heating operation time is 5-50 seconds. 4) Spray drying The final emulsion was spray-dried to obtain β-carotene powder; In steps 1) and 2), based on the total mass of the following raw materials as 100%, the percentages of each raw material are as follows: β-carotene 0.1-10%, Oil phase antioxidant 1-10%, Stabilizer 0.01-1%, Oil content 1-20%, Lipase 0.01-0.2%, Water-soluble colloids 10-60%, Carbohydrate fillers 20-70%, Aqueous antioxidant 1-8%, Acidity regulator 0.1-1%.
2. The method for preparing high bioavailability yellow β-carotene powder according to claim 1, characterized in that, In steps 1) and 2), based on the total mass of the following raw materials as 100%, the percentages of each raw material are as follows: β-carotene 1-5%, Oil phase antioxidant 2-5%, Stabilizer 0.1-0.5%, Oil content 5-10%, Lipase 0.05-0.1%, Water-soluble colloids 30-50%, Carbohydrate fillers 30-55%, Aqueous antioxidant 2-5%, Acidity regulator 0.1-0.5%.
3. The method for preparing high bioavailability yellow β-carotene powder according to claim 2, characterized in that, In step 2), the amount of pure water used is 1-2 times the total mass of the above raw materials.
4. The method for preparing high bioavailability yellow β-carotene powder according to any one of claims 1-3, characterized in that, The oil phase antioxidant is one or more of butylated hydroxytoluene, butylated hydroxyanisole, tert-butylhydroquinone, tocopherol, and vitamin C palmitate.
5. The method for preparing high bioavailability yellow β-carotene powder according to claim 4, characterized in that, The stabilizer is one or more of zinc laurate, zinc caprylate, and zinc benzoate.
6. The method for preparing high bioavailability yellow β-carotene powder according to claim 5, characterized in that, The oil is one or more of corn oil, soybean oil, sunflower seed oil, rapeseed oil, and caprylic / capric triglycerides.
7. The method for preparing high bioavailability yellow β-carotene powder according to any one of claims 1-3, characterized in that, The water-soluble colloid is one or more of gelatin, sodium lignosulfonate, calcium lignosulfonate, sodium octenyl succinate starch, and gum arabic.
8. The method for preparing high bioavailability yellow β-carotene powder according to claim 7, characterized in that, The sugar filler is one or more of sucrose, glucose, glucose syrup, maltodextrin, fructose, xanthodextrin, and maltodextrin.
9. The method for preparing high bioavailability yellow β-carotene powder according to claim 8, characterized in that, The aqueous antioxidant is one or more of ascorbic acid, sodium ascorbate, and isoascorbic acid.
10. The method for preparing high bioavailability yellow β-carotene powder according to claim 9, characterized in that, The acidity regulator is one or more of sodium citrate, potassium citrate, sodium lactate, sodium acetate, and potassium acetate.
11. The method for preparing high bioavailability yellow β-carotene powder according to claim 10, characterized in that, The amount of the acidity regulator used is such that the pH of the aqueous phase is 4.5-6.
12. The method for preparing high bioavailability yellow β-carotene powder according to any one of claims 1-3, characterized in that, In step 3), the high-speed shearing conditions are: rotation speed 3000-8000 rpm, time 10-30 min.
13. The method for preparing high bioavailability yellow β-carotene powder according to claim 12, characterized in that, In step 3), the gauge pressure for high-pressure homogenization is 30-100 MPa.
14. The method for preparing high bioavailability yellow β-carotene powder according to claim 13, characterized in that, In step 3), the gauge pressure for high-pressure homogenization is 50-60 MPa.