CN102796398B - Preparation method of beta-carotene microcapsule used for coloring - Google Patents

Abstract

The invention discloses a preparation method of beta-carotene microcapsules. Various solvents are used in most existing methods, wherein some solvents such as grease will exist all the time with products after high temperature treatment, and most of the methods have complex technology and use a lot of raw materials. The method comprises: dispersing 100 parts of dry basis waxy corn starch to 30%-40% of starch milk by adding water, and after adjusting the pH value to be 5.5-6.5, enzymatically hydrolyzing in the presence of 0.1-1 parts of high temperature resistance alpha-amylase at the temperature of 75-90 DEG C for 10-30 minutes; and then adding the melts of 1-10 parts of beta-carotene, 1-3 parts of octenyl succinic anhydride and 0-30 parts of plant oil dropwise in a uniform speed to the obtained starch milk within 30-90 minutes under the protection of nitrogen, and after the addition, proceeding to shearing emulsification for 30-60 minutes and maintaining the pH value of the system being 8-9. The method uses low-cost raw materials to replace commercial emulsification embedding materials for directly preparing the beta-carotene microcapsules, with simple technology and saved cost.

Description

A kind of preparation method for painted β-carotene microcapsule

Technical fieldThe present invention relates to the preparation of carotenoid, specifically a kind of for painted β-carotene

The preparation method of microcapsule.

Background technology

Carotenoid (Carotenoids) extensively is present in occurring in nature, and current business-like carotenoid product mainly contains β-carotene, astaxanthin, Lyeopene and canthaxanthin etc.These materials are widely used in the fields such as food, makeup, feed and medicine industry as nutrition-fortifying agent and tinting material.Carotenoid is water insoluble, and solubleness is also very little in oil, and all very responsive to light, heat and oxygen, can't directly apply.Generally all need carotenoid crystallization super-refinement, and with protective colloid, make the dosage forms such as microcapsule and could apply.Carotenoid can significantly improve bioavailability after preparation, improve coloring effect and reduce consumption.

Report about the preparation method of β-carotene and carotenoid formulation mainly contains following several:

WO91/06292 and WO94/19411 have introduced and have used colloidal mill β-carotene to be ground to form to the particulate of 2～10 μ m, and then drying is made the carotenoid powder of water-dispersion.

US3998753 has put down in writing the dispersible carotenoid preparation method of a kind of water, and wherein the particle diameter of carotenoid is less than 1 μ m.The method first is made into carotenoid and other additive the solution of organic solvent, then joins in the aqueous solution that contains gelatin, dispersion agent, stablizer, makes the System forming emulsion through high speed shear; Remove organic solvent and spraying drying obtains desired product.

The method of the carotenoid powder of the preparation water-dispersion that EP0065193 puts down in writing, in 50～200 ℃, to be dissolved in carotenoid in the mixable solvent of volatile water in 10 seconds, then under 0～50 ℃ with contain the aqueous solution short mix of protective colloid, carotenoid namely with the size dispersion that is less than 0.5 μ m in protective colloid, desolvation dry carotenoid powder; CN102361561A namely uses stable suspension by what similar technique prepared part amorphous-type carotene particle.

CN101828693A obtains carotenoid oil suspension by utilizing tetrahydrofuran (THF), ethanol, plant wet goods to process carotenoid; CN102341002A is also that utilization changes the art breading carotenoid oil suspension and obtains carotenoid solutions.

CN102281859A has disclosed a kind of preparation method of emulsion compositions, is mainly the grease phase that is dissolved with in advance carotenoid is mixed to get with the water that contains numerous emulsifiers; CN101312655B has also adopted similar technique and the emulsion spraying drying has been obtained to product.

CN1233169A has reported two kinds for the treatment of with supercritical fluid techniques: A technique is first carotenoid to be dissolved in overcritical dme under High Temperature High Pressure, and then explosive decompression obtains Powdered carotenoids crude granule; B technique is first carotenoid to be dissolved under High Temperature High Pressure in subcritical or postcritical pressurized gas, then by this Solution Dispersion in other batching, then make powder preparation after will the pressurized gas in this mixed solution removing.

US6056791 has also reported a kind of technique, under certain pressure, carotenoid is mixed with supercutical fluid, until form the solution that contains the 5%-90% supercutical fluid.The fusing point of selected supercutical fluid is than low 40 ℃ at least of the fusing points of carotenoid.Then temperature is adjusted to than supercritical flow bulk melting point to high or low 50 ℃, and by Pressure Drop to normal atmosphere.Supercutical fluid gasifies rapidly with this understanding, and the particle diameter of carotenoids crude granule can reach 0.7 μ m-5 μ m simultaneously.

In DE2943267, mention, β-carotene is dissolved in to explosive decompression after supercutical fluid, obtain the fine particle β-carotene, then add other batching to make solid chemicals.

Applicant of the present invention also applies for a series of patents successively, comprises the preparation method (publication number CN101879428A) of the carotenoid microcapsules that the preparation method (publication number CN101549273A) of high-all-trans-carotenoid microcapsules of nano-dispersed of the preparation method (publication number CN101016259A) of a kind of high content full cis-beta-carotene preparation of the preparation method (publication number CN1836652A) of a kind of water-dispersed carotenoid powder of application in 2005, application in 2007, application in 2009 and the isomer proportion applied in 2010 are controlled.

In above-mentioned bibliographical information, all adopt different emulsification embedded materials that carotenoid is made to emulsion or microcapsule, but in the preparation process, all use existing commodity emulsification embedded material, thereby cost is higher.

In the production process of numerous carotenoid products, starch octenyl succinate anhydride is a kind of emulsification embedding medium commonly used, and its preparation principle is based on esterification can carry out under gentle alkaline condition.This product was listed in U.S. food additive category in 1972 by U.S. food and FAD (FDA), was also current unique starch alkenyl succinate ester product that is allowed for foodstuff additive by FDA.Starch octenyl succinate anhydride now has been included China and has used in interior Main Countries approval, and when its quality index was production food grade starch octenyl succinate anhydride, it was 3% that the maximum of octenyl succinic acid anhydride allows usage quantity.

About starch octenyl succinate anhydride preparation method's report, mainly contain following several:

At first nineteen fifty-three Caldwell and Wurzburg have disclosed the preparation method of starch octenyl succinate anhydride in US2661349A, its basic procedure comprises: starch is made into to certain density starch milk, then slowly add the octenyl succinic acid anhydride through alcohol dilution, controlling simultaneously the pH value is 8～9; The acid adding adjust pH was to slightly acidic after reaction finished, then through repeatedly washing, dry, obtain product after pulverizing, sieving.This is classical wet method preparation process, by most people, is continued to use in decades always.On this method basis, also derived technique prepared by a series of wet methods, comprise that the present patent application people prepares the method (publication number CN102276741A) of starch ester in the recycle octenyl succinic acid anhydride of application in 2011.

In addition, KR100857290 has introduced a kind of method that dry heating method prepares starch octenyl succinate anhydride, at first the method is hydrolyzed octenyl succinic acid anhydride, then with starch, mix and mixture is dried to water content being less than 10%, then at high temperature heating causes the replacement of Starch Hydrolysis and octenyl succinic; After WO2010/091091A2 had also reported starch is mixed with acid anhydrides, pyroprocessing obtained the method for starch octenyl succinate anhydride.

Summary of the invention

The objective of the invention is the problem for above-mentioned existence, in conjunction with the common part in carotenoid formulation and starch octenyl succinate anhydride preparation method, provide a kind of waxy corn starch, octenyl succinic acid anhydride, β-carotene and vegetables oil method for the preparation of painted β-carotene microcapsule of directly utilizing.

For this reason, the present invention adopts following technical scheme: a kind of preparation method for painted β-carotene microcapsule, it is characterized in that comprising the following steps, following umber all by mass:

1) 100 parts of butt waxy corn starchs being added to water-dispersion, to become the quality percentage composition be 30%～40% starch milk, then add 0.1～1 part of high temperature resistant α-amylase, regulate pH value to 5.5～6.5, in 75～90 ℃ of lower enzymolysis 10～30 minutes, then regulate pH value to 8～9;

2) in advance by 1～10 part of β-carotene, 1～3 part of octenyl succinic acid anhydride and 0～30 part of vegetables oil 120 ℃～160 ℃ lower meltings, then under nitrogen atmosphere protection, at the uniform velocity be added drop-wise in the starch milk of step 1) gained in 30～90 minutes, this starch milk is in 5000～10000r/min high speed shear, drip rear continuation emulsification pretreatment 30～60 minutes, and the pH value of omnidistance maintenance system is 8～9;

3), after emulsification, regulate pH value to 6.5～7.5, then obtain the β-carotene microcapsule through homogeneous, spraying drying.

Described vegetables oil is soybean oil, Semen Maydis oil, sunflower seed oil, peanut oil or salad oil.

The invention has the beneficial effects as follows: with the commodity of raw material replacement cheaply emulsification embedded material, directly prepare the β-carotene microcapsule, technique is simple and cost-saving; Preparation process is not brought any solvent into, and Product Safety is high; In microcapsule, the carotenoid particle diameter reaches 0.2～1.5 μ m, and bioavailability is high.

Embodiment

The invention will be further described below in conjunction with embodiment.

Embodiment 1

Preparation method for painted β-carotene microcapsule is as follows:

(1) 100kg butt waxy corn starch adds water-dispersion and becomes 30% starch milk, then adds the high temperature resistant α-amylase of 0.1kg (enzyme activity 20000u/g), regulates pH value to 5.5, in 90 ℃ of lower enzymolysis 30 minutes, then regulates pH value to 8;

(2) in advance by 1kg β-carotene and 1kg octenyl succinic acid anhydride 160 ℃ of lower meltings, then under nitrogen atmosphere protection, at the uniform velocity be added drop-wise in 30 minutes in the described starch milk of step (1) under the 5000r/min high speed shear, drip rear continuation emulsification pretreatment 60 minutes, and the pH value of utilizing the omnidistance maintenance system of pH value controller is 8;

(3) regulate pH value to 7, then obtain through homogeneous, spraying drying that content is 0.8%, volume average particle size is the β-carotene microcapsule of 0.2 μ m.

Embodiment 2

Preparation method for painted β-carotene microcapsule is as follows:

(1) 100kg butt waxy corn starch adds water-dispersion and becomes 40% starch milk, then adds the high temperature resistant α-amylase of 1kg (enzyme activity 25000u/g), regulates pH value to 6.5, in 75 ℃ of lower enzymolysis 10 minutes, then regulates pH value to 9;

(2) in advance by 10kg β-carotene, 3kg octenyl succinic acid anhydride and 30kg soybean oil 120 ℃ of lower meltings, then under nitrogen atmosphere protection, at the uniform velocity be added drop-wise in 90 minutes in the described starch milk of step (1) under the 10000r/min high speed shear, drip rear continuation emulsification pretreatment 30 minutes, and the pH value of utilizing the omnidistance maintenance system of pH value controller is 9;

(3) regulate pH value to 7.5, then obtain through homogeneous, spraying drying that content is 4.7%, volume average particle size is the β-carotene microcapsule of 1.5 μ m.

Embodiment 3

Preparation method for painted β-carotene microcapsule is as follows:

(1) 100kg butt waxy corn starch adds water-dispersion and becomes 35% starch milk, then adds the high temperature resistant α-amylase of 0.5kg (enzyme activity 23000u/g), regulates pH value to 6, in 80 ℃ of lower enzymolysis 20 minutes, then regulates pH value to 8.5;

(2) in advance by 5kg β-carotene, 3kg octenyl succinic acid anhydride and 20kg Semen Maydis oil 130 ℃ of lower meltings, then under nitrogen atmosphere protection, at the uniform velocity be added drop-wise in 50 minutes in the described starch milk of step (1) under the 7000r/min high speed shear, drip rear continuation emulsification pretreatment 40 minutes, and the pH value of utilizing the omnidistance maintenance system of pH value controller is 8.5;

(3) regulate pH value to neutrality, then obtain through homogeneous, spraying drying that content is 3.1%, volume average particle size is the β-carotene microcapsule of 0.9 μ m.

Embodiment 4

Preparation method for painted β-carotene microcapsule is as follows:

(1) 100kg butt waxy corn starch adds water-dispersion and becomes 40% starch milk, then adds the high temperature resistant α-amylase of 0.2kg (enzyme activity 19000u/g), regulates pH value to 6.3, in 85 ℃ of lower enzymolysis 25 minutes, then regulates pH value to 8.5;

(2) in advance by 8kg β-carotene, 2.5kg octenyl succinic acid anhydride and 10kg sunflower seed oil 140 ℃ of lower meltings, then under nitrogen atmosphere protection, at the uniform velocity be added drop-wise in 60 minutes in the described starch milk of step (1) under the 8000r/min high speed shear, drip rear continuation emulsification pretreatment 50 minutes, and the pH value of utilizing the omnidistance maintenance system of pH value controller is 8.5;

(3) regulate pH value to neutrality, then obtain through homogeneous, spraying drying that content is 5.1%, volume average particle size is the β-carotene microcapsule of 1.1 μ m.

Embodiment 5

Preparation method for painted β-carotene microcapsule is as follows:

(1) 100kg butt waxy corn starch adds water-dispersion and becomes 38% starch milk, then adds the high temperature resistant α-amylase of 0.3kg (enzyme activity 18000u/g), regulates pH value to 6.5, in 85 ℃ of lower enzymolysis 20 minutes, then regulates pH value to 9;

(2) in advance by 3.2kg β-carotene, 2.4kg octenyl succinic acid anhydride and 4kg peanut oil 150 ℃ of lower meltings, then under nitrogen atmosphere protection, at the uniform velocity be added drop-wise in 45 minutes in the described starch milk of step (1) under the 9000r/min high speed shear, drip rear continuation emulsification pretreatment 45 minutes, and the pH value of utilizing the omnidistance maintenance system of pH value controller is 9;

(3) regulate pH value to neutrality, then obtain through homogeneous, spraying drying that content is 2.5%, volume average particle size is the β-carotene microcapsule of 0.8 μ m.

Claims (2)

1. the preparation method for painted β-carotene microcapsule, is characterized in that comprising the following steps, following umber all by mass:

1) 100 parts of butt waxy corn starchs being added to water-dispersion, to become the quality percentage composition be 30%～40% starch milk, then add 0.1～1 part of high temperature resistant α-amylase, regulate pH value to 5.5～6.5, in 75～90 ℃ of lower enzymolysis 10～30 minutes, then regulate pH value to 8～9;

2) in advance by 1～10 part of β-carotene, 1～3 part of octenyl succinic acid anhydride and 0～30 part of vegetables oil 120 ℃～160 ℃ lower meltings, then under nitrogen atmosphere protection, at the uniform velocity be added drop-wise in the starch milk of step 1) gained in 30～90 minutes, this starch milk is in 5000～10000r/min high speed shear, drip rear continuation emulsification pretreatment 30～60 minutes, and the pH value of omnidistance maintenance system is 8～9;

3), after emulsification, regulate pH value to 6.5～7.5, then obtain the β-carotene microcapsule through homogeneous, spraying drying.

2. the preparation method for painted β-carotene microcapsule according to claim 1, is characterized in that, described vegetables oil is soybean oil, Semen Maydis oil, sunflower seed oil, peanut oil or salad oil.