CN100421650C - Preparation method of water-dispersible carotenoid powder - Google Patents

Abstract

The invention relates to a method for preparing water-dispersible carotenoid powder. Existing solvent method or high temperature solvent method all need to remove a large amount of solvent in the protective colloid, the system is very easy to foam, and it is difficult to control the particle size and color of carotenoid powder. The steps of the present invention are as follows: the crude crystals of carotenoids are dissolved in halogenated hydrocarbons or ester solvents containing antioxidants and emulsifiers, and added in the form of spraying to stirred ethanol or isopropanol, so that the carotenoids Precipitate in the form of amorphous powder; filter the precipitated carotenoids with a filter membrane or a sintered filter stick, wash the filter cake with ethanol or isopropanol, and filter dry; add the filter cake to an aqueous solution containing a protective colloid, first stir and beat, and then pass through Homogeneous emulsification, and then remove the residual solvent to make a water dispersion; the dispersion is granulated by spraying, and then dried by fluidization. The invention is easy to remove the solvent, has less residual amount, is quick to remove, has high efficiency, and is easy to control the particle size and color of the required carotenoids.

Description

Preparation method of water-dispersible carotenoid powder

technical field

The invention relates to the preparation of carotenoid powder, in particular to a preparation method of water-dispersible carotenoid powder.

Background technique

Carotenoids widely exist in nature, the most important representatives of which are β-carotene, astaxanthin, and canthaxanthin. These substances are important coloring agents for food, cosmetics, feed, and pharmaceutical industries. In addition, some of them are also precursors of vitamin A. Carotenoids are insoluble in water and have little solubility in oil, and most carotenoids are sensitive to heat and oxygen, so they cannot be directly used in coarse crystals and are difficult to be absorbed by animals. Whether it is used in food or other fields, carotenoids generally need to exist in the form of fine particles and need to be protected with protective colloids to resist oxidation. For the purpose of coloring, it is hoped that the carotenoids can increase the bioavailability after formulation, so as to improve the coloring effect, reduce the dosage, and reduce the loss during use.

In use, it is often necessary to formulate carotenoids into water-dispersible formulations. For this purpose, some literatures have reported the preparation methods of such preparations.

WO91/06292 and WO94/19411 have introduced the use of colloid mill to grind β-carotene into 2-10 μm particles, and then dry to make water-dispersed carotenoid powder. However, the grinding method has low efficiency and high energy consumption, and the particle size of carotenoids is difficult to reach below 1 μm.

US3998753 describes a method for preparing water-dispersible carotenoids, wherein the particle size of carotenoids is less than 1 μm. The method is to first make carotenoids and other additives into a solution of an organic solvent, and then add the carotenoids containing gelatin, dispersant 1. In the aqueous solution of the stabilizer, the system is formed into an emulsion by high-speed shearing; the organic solvent is removed, and the required powder is obtained by spray drying.

The method for preparing water-dispersed carotenoid powder described in EP-0065193 (or US4522743) is to dissolve the carotenoid in a volatile water-miscible solvent within 10 seconds at 50-200° C. Quickly mix with an aqueous solution containing a protective colloid at ~50°C, the carotenoids are dispersed in the protective colloid with a size of <0.5 μm, the solvent is removed, and the carotenoid powder is obtained by drying. This process needs to be carried out under high-pressure equipment (pressure 3.0-6.0MPa) and high temperature (170-200°C), which requires high equipment and is difficult to operate and control.

The above solvent method or high temperature solvent method all need to remove a large amount of solvent contained in the system in the protective colloid, which takes a long time and is not easy to remove completely. In addition, in the presence of the protective colloid, the system is prone to foaming and desolvation. The efficiency of dissolution is very low, and it is difficult to control the particle size and color of the required carotenoid powder.

Contents of the invention

The technical problem to be solved by the present invention is to overcome the above-mentioned defects in the prior art and provide a method for preparing water-dispersible carotenoid powder which is easy to remove the solvent and control the required particle size and color.

For this reason, the present invention adopts the following technical solutions: the preparation method of water-dispersible carotenoid powder is characterized in that comprising the following steps: 1) dissolving the crude carotenoid crystals in halogenated hydrocarbons or halogenated hydrocarbons containing antioxidants and emulsifiers In the ester solvent, the resulting solution is added to the stirring ethanol or isopropanol in the form of a spray, so that the carotenoids are separated out in the form of amorphous powder; The cake is washed with ethanol or isopropanol, and filtered dry; 3) Add the filter cake into an aqueous solution containing protective colloid, first stir and beat, then homogeneously emulsify, then remove residual solvent, and then make an aqueous dispersion ; 4) The dispersion liquid is granulated by spraying method, and then dried by fluidization. The core of the present invention is to add the carotenoid solution containing antioxidant and dispersant to the ethanol or isopropanol stirred at a high speed in the form of spraying with a high-pressure pump, so that the carotenoid is separated out in the form of amorphous powder, The particle size and color of the precipitated carotenoid powder can be controlled by adjusting the concentration of carotenoid solution, the size of spray droplets, and the speed of stirring. Low concentration, small droplet size and fast stirring are all conducive to the formation of carotenoids with small particle size. pink. The particle size of the water-dispersible carotenoid powder finally obtained in the present invention is less than 2 μm.

In the preparation method of the water-dispersible carotenoid powder, the stirring speed is controlled at ≥ 500 rpm.

In the preparation method of the water-dispersible carotenoid powder, the pore diameter of the filter membrane or the sintered filter rod is less than 0.3 μm.

In the preparation method of the water-dispersible carotenoid powder, the halogenated hydrocarbon is dichloromethane, chloroform or dichloroethane.

In the preparation method of the water-dispersible carotenoid powder, the esters are ethyl acetate, propyl acetate, isopropyl acetate or butyl acetate.

In the preparation method of the water-dispersible carotenoid powder, the emulsifier is fatty acid glyceride or Span.

In the preparation method of the water-dispersible carotenoid powder, the antioxidant is ethoxyquin or tocopherol.

In the preparation method of the water-dispersible carotenoid powder, the protective colloid is gelatin, fish gelatin or modified starch.

In the preparation method of the water-dispersible carotenoid powder, the carotenoid is β-carotene, astaxanthin or canthaxanthin.

The beneficial effects of the present invention are: basically do not need high-pressure equipment and operate under normal conditions, low equipment requirements, relatively simple operation and control; easy to remove solvent, less residue, fast removal, high efficiency; easy to control the required carotenoid particle size and color.

The present invention will be described in detail below in conjunction with the examples.

Detailed ways

Example 1

Dissolve 100 g of astaxanthin crude crystals, 10 g of ethoxyquin, and 20 g of monoglyceride stearate in 3 L of dichloromethane to prepare an astaxanthin solution. Add 20L ethanol to a 50L kettle equipped with high-speed stirring (≥500rpm), start stirring, then use a high-pressure pump to slowly add the above-mentioned astaxanthin solution into the kettle in the form of spray through the nozzle, and adjust the spray speed so that all The diameter of the precipitated amorphous astaxanthin particles is less than 2 μm. After spraying, use a microporous membrane filter with a pore size of 0.3 μm to filter, wash the filter cake with ethanol, and dry it to obtain ultrafine amorphous astaxanthin. Powder (average particle size 0.9 μm) filter cake. Mix the above filter cake with an aqueous solution containing 300g gelatin, 100g sucrose, 10g VC sodium salt, and 2500ml water, stir and make a slurry, and then homogenize in a high-pressure homogenizer for 5 hours. Granulate in a granulator and dry in a fluidized bed to obtain water-dispersible astaxanthin powder containing 12.1% astaxanthin.

Example 2

Heat and dissolve 50g of β-carotene crude crystals, 10g of tocopherol, and 10g of Span-60 in 2L of butyl acetate to make a β-carotene solution. Add 20L isopropanol and 2L water in a 50L kettle with high-speed stirring (3500rpm), start stirring, then use a high-pressure pump to slowly add the above-mentioned β-carotene solution to the kettle in the form of a spray, adjust the spray speed, so that Precipitated particle diameter <2μm. Filtrate with a sintered filter rod with a pore diameter of 0.3 μm, wash the filter cake with 90% isopropanol, and press dry to obtain an ultrafine β-carotene amorphous powder (average particle diameter of 0.7 μm) filter cake. Mix the above filter cake with an aqueous solution containing 200g of modified starch, 5g of VC sodium salt, and 1500ml of water, stir and beat, and then homogenize in a high-pressure homogenizer for 10 hours. The bed is dried to obtain water-dispersible β-carot powder containing 10.5% of β-carotene.

Example 3

Heat and dissolve 100g of canthaxanthin crude crystals, 20g of tocopherol, 10g of ethoxyquin, and 15g of Span-40 in 3L of chloroform to form a solution. Add 20L of 95% ethanol into a 50L kettle equipped with high-speed stirring, start stirring, then slowly add the above solution into the kettle in the form of spray with a high-pressure pump, and adjust the spray speed so that the diameter of the precipitated particles is less than 2 μm. Filtrate with a sintered filter stick with a pore diameter of 0.3 μm, wash the filter cake with 95% ethanol, and press dry to obtain a cantharidin filter cake with an average particle size of 0.55 μm. Mix the above filter cake with an aqueous solution containing 300g fish gelatin, 100g sucrose, 20g VC sodium salt, and 2500ml water, stir and beat, then homogenize in a high-pressure homogenizer for 5 hours, remove the residual solvent from the emulsified dispersion in a vacuum, and spray Granulation, fluidized drying to obtain water-dispersible cantharidin powder with a content of 11.3%.

Claims (10)

1. The preparation method of water-dispersible carotenoid powder is characterized in that comprising the following steps: 1) dissolving the crude carotenoid crystals in halogenated hydrocarbons or ester solvents containing antioxidants and emulsifiers, and the resulting solution Spray into the stirred ethanol or isopropanol to precipitate carotenoids in the form of amorphous powder, and control the precipitated carotenoids by adjusting the concentration of carotenoid solution, the size of spray droplets, and the speed of stirring The particle size of the powder is less than 2 μm; 2) filter the precipitated carotenoids with a filter membrane or a sintered filter stick, wash the filter cake with ethanol or isopropanol, and filter to dry; 3) add the filter cake to an aqueous solution containing a protective colloid 4) The dispersion liquid is granulated by spraying method, and then dried by fluidization. 2. The preparation method of water-dispersible carotenoid powder according to claim 1, characterized in that the stirring speed is controlled at ≥ 500 rpm. 3. The preparation method of water-dispersible carotenoid powder according to claim 1, characterized in that the aperture of the filter membrane or sintered filter rod is less than 0.3 μm. 4. the preparation method of water-dispersible carotenoid powder according to claim 1, is characterized in that described halogenated hydrocarbon is methylene chloride, chloroform or ethylene dichloride. 5. the preparation method of water-dispersible carotenoid powder according to claim 1 is characterized in that described ester is ethyl acetate, propyl acetate, isopropyl acetate or butyl acetate. 6. the preparation method of water-dispersible carotenoid powder according to claim 1 is characterized in that described emulsifier is fatty acid glyceride or Span. 7. the preparation method of water-dispersible carotenoid powder according to claim 1, is characterized in that described antioxidant is ethoxyquin or tocopherol. 8. the preparation method of water-dispersible carotenoid powder according to claim 1, is characterized in that described protective colloid is gelatin or modified starch. 9. the preparation method of water-dispersible carotenoid powder according to claim 8, is characterized in that described protective colloid is fish gelatin. 10. The preparation method of water-dispersible carotenoid powder according to claim 1, wherein said carotenoid is β-carotene, astaxanthin or canthaxanthin.