CN101744790A - Method for preparing stable-type vitamin A microcapsules continuously - Google Patents

Method for preparing stable-type vitamin A microcapsules continuously Download PDF

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Publication number
CN101744790A
CN101744790A CN201010101199A CN201010101199A CN101744790A CN 101744790 A CN101744790 A CN 101744790A CN 201010101199 A CN201010101199 A CN 201010101199A CN 201010101199 A CN201010101199 A CN 201010101199A CN 101744790 A CN101744790 A CN 101744790A
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vitamin
microcapsules
gelation
modified starch
emulsion
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CN101744790B (en
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尹红
陈建峰
陈志荣
王洁欣
祁勇
赵宏
石立芳
仇丹
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Beijing University of Chemical Technology
Zhejiang University ZJU
Zhejiang NHU Co Ltd
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Beijing University of Chemical Technology
Zhejiang University ZJU
Zhejiang NHU Co Ltd
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Abstract

The invention discloses a method for preparing vitamin A microcapsules continuously and stably, comprising the following steps: Adding vitamin A crystals and an antioxidant in a crystal melter continuously according to a certain ratio under the protection of nitrogen to prepare vitamin A melting oil containing the antioxidant; pumping the above melting oil in a supergravity rotary packed bed emulsifier by a pump, and pumping aqueous solution containing modified gelation starch into the above supergravity rotary packed bed emulsifier after deoxidation treatment to obtain vitamin A emulsion at the outlet of the supergravity rotary packed bed emulsifier; and atomizing and spraying the emulsion in a cooled starch bed for pelletizing, and performing fluidization drying and gelation treatment in a fluidized bed by taking nitrogen as a drying medium to obtain the stable-type vitamin A microcapsules. The invention has the advantage of capability of continuous production, and has good embedding effect due to adopting the modified gelation starch, pelletizing and gelation treatment, thus the product has good storage stability.

Description

A kind of preparation method of stable-type vitamin A microcapsules continuously
Technical field
The present invention relates to a kind of preparation method of stable-type vitamin A microcapsules continuously, be specifically related to adopt hypergravity RPB emulsator to carry out the preparation of stable-type vitamin A microcapsules continuously.
Background technology
Vitamin A is a kind of fatsoluble vitamin, is soluble in organic solvent and fat, and is water insoluble.All perishable when vitamin A is met light, heat, acid, oxidant, could use so generally need be made into microencapsulation form.
The micro encapsulation of vitamin A normally earlier with the vitamin A crystallization, join oil with the aqueous solution that contains protecting colloid heat, emulsifying, again the emulsion spray drying is obtained.
Chinese patent CN1965657 (A) has introduced a kind of method for preparing type vitamin A microcapsules, this method joins vitamin A oil in the modified starch solution that prepared in advance before several hours, high speed dispersion emulsifying under 5000~20000rpm rotating speed, homogenizing twice under room temperature, 10~40MPa then, last centrifugal spray drying obtains type vitamin A microcapsules.Because the products obtained therefrom particle diameter is thin, be mainly used in the reinforcement of flour.
Chinese patent CN101214219 (A) has then reported the method for preparing vitamin A, Vitamin E contained micro capsule, and its emulsion process has been used the high speed shear of 10000~20500rpm, and needs under 40~60MPa homogenizing 3 times, then spray-dried preparation microcapsule.
The above-mentioned high speed shear emulsifying homogenizing that adds high pressure, the problem that is difficult to overcome below the spray-dried then method for preparing type vitamin A microcapsules exists:
1) emulsion process is carried out and in open environment, single batch of emulsification times is long in batches, and cut part megadyne temperature degree height during emulsifying easily makes vitamin A rotten;
2) high-speed shearing machine and high pressure homogenizer required motor power are big, the energy consumption height;
3) owing to batch operation, the easy layering of emulsion in spray-drying process after emulsifying is finished, the easy coalescence of the little oil droplet of accumulative vitamin A becomes bulky grain, thereby influences the embedding effect and the bioavailability of final products.
4) the high pressure homogenize method is difficult to make vitamin A to be scattered in the microcapsule with nano-grade size, thereby has had influence on the use in some products.
At the problems referred to above, the inventor has proposed a kind of preparation method of serialization nanometer dispersed vitamin A microcapsule in CN101513394A.This method is ground vitamin A crystal earlier and is made into the vitamin A dispersion liquid with antioxidant, solvent; with pump above-mentioned dispersion liquid is dissolved postcooling through pre-heating temperature elevation then; send into again in the high-gravity rotating bed crystallize device; the aqueous solution that will contain protecting colloid is simultaneously sent in the same high-gravity rotating bed crystallize device; outlet obtains the vitamin A dispersion liquid of nano-dispersed; with this dispersion liquid spray drying in the spray dryer that has the fluidization chiller, promptly obtain the type vitamin A microcapsules of nano-dispersed.The means of high-gravity rotating bed crystallize device as the vitamin A nanorize are adopted in this invention, make the bioavailability of vitamin A improve, and the product applicable surface enlarges.
But vitamin A is a kind of vitamin of fat-soluble, poor stability, even spray-dried micro encapsulation, in the storage of product, owing to be subjected to the influence of light, heat, oxidant, acid, its effective content still can obviously descend.By further research, we find that if can avoid being heated for a long time, the touch opportunity of minimizing and oxygen increases the outer field resistance oxygen of microcapsule, the measure that blocks water simultaneously as far as possible, then can effectively improve the stability of vitamin A in the micro encapsulation process of vitamin A.
Summary of the invention
The objective of the invention is weak point, but the invention provides a kind of preparation method of quantity-produced stable-type vitamin A microcapsules at existing type vitamin A microcapsules production technology.
The preparation method of stable-type vitamin A microcapsules continuously may further comprise the steps:
1) under nitrogen protection, vitamin A crystallization, antioxidant are added in the watery fusion device continuously by 100: 1~5 part by weight, in 65~75 ℃ of fusings, be made into the vitamin A melting oil that contains antioxidant;
2) but the gelation modified starch is dissolved in 65~75 ℃ of water, be made into 30~40% modified starch aqueous solutions, and in-0.07~-the 0.08MPa vacuum under deoxygenation 1~2 hour;
3) vitamin A melting is oily with being pumped in the hypergravity RPB emulsator that has liquid distribution trough; Simultaneously, the modified starch aqueous solution after the deoxygenation with being pumped in the same hypergravity RPB emulsator, is obtained the vitamin A emulsion in outlet, vitamin A melting oil is 1: 3~9 with the weight ratio of modified starch aqueous solution;
4) with the vitamin A emulsion continuously atomizing spray into and carry out pelletize in the cooled starch bed, then with nitrogen as the fluid bed of drying medium in 65~75 ℃ carry out fluidized drying, gelation is handled, and promptly obtains stable-type vitamin A microcapsules.
Described antioxidant is ethoxy quinoline, tocopherol, BHT or BHA.
Described hypergravity RPB emulsator has liquid distribution trough, and filler is a metal gauze, and rotating speed is 1500~2500 rev/mins.
The beneficial effect that the present invention compared with prior art has:
1) but to adopt the gelation modified starch be main embedded material, handle through mist projection granulating, fluidized drying and gelation again, thereby product produced the double shielding effect, its embedding is effective, is difficult for the moisture absorption;
2) adopt hypergravity RPB emulsator continuous emulsification, the vitamin A particle size is even in the emulsion, has avoided the generation of the low megacryst of bioavailability;
3) sufficient nitrogen protection of production process and deoxygenation measure have guaranteed that vitamin A never degenerates in the production process, and micro encapsulation process yield height has so not only also increased simultaneously the bin stability of product.
Below in conjunction with embodiment the present invention is described in detail.
The specific embodiment
Embodiment 1
Under nitrogen protection, the vitamin A crystallization is added in the special watery fusion device with 0.5Kg/ hour with 10Kg/ hour, antioxidant ethoxy quinoline, make watery fusion in 65 ℃, obtain 10.5Kg/ hour vitamin A melting oil.
But gelation modified starch 567Kg is dissolved in the 1323Kg65 ℃ of water, is made into 30% modified starch aqueous solution, and in-0.08MPa the degassing 2 hours.
The molten oil of said vitamin A sent into 10.5Kg/ hour flow with pump to have liquid distribution trough, rotating speed be in 1500 rev/mins the hypergravity RPB emulsator, simultaneously the modified starch aqueous solution after the deoxygenation is sent in the same hypergravity RPB emulsator with 94.5Kg/ hour flow, obtained the vitamin A emulsion from outlet.
The continuous atomizing of said vitamin A emulsion is sprayed into pelletize in the cooled starch bed, after 20 hours, obtain the wet type vitamin A microcapsules of about 2800Kg.
Above-mentioned wet type vitamin A microcapsules is forwarded in the fluid bed, carry out fluidized drying and gelation processing, obtain the 1010Kg type vitamin A microcapsules at last with 65 ℃ of hot nitrogens.Analyze through HPLC, wherein the content of vitamin A is 19.62%, and the micro encapsulation yield is 99.08%.Behind the storage at normal temperature 2 years, content is 19.05%, and the vitamin A retention rate is 97.1%.
But the gelation modified starch is the CAPSUL 2330 that National Starch (national of the United States's starch company limited) produces.
Embodiment 2
Under nitrogen protection, the vitamin A crystallization is added in the special watery fusion device with 0.3Kg/ hour with 10Kg/ hour, antioxidant tocopherol, make watery fusion in 70 ℃, obtain 10.3Kg/ hour vitamin A melting oil.
But gelation modified starch 247.2Kg is dissolved in the 370.8Kg75 ℃ of water, is made into 40% modified starch aqueous solution, and in-0.07MPa the degassing 1 hour.
The molten oil of said vitamin A sent into 10.3Kg/ hour flow with pump to have liquid distribution trough, rotating speed be in 2500 rev/mins the hypergravity RPB emulsator, simultaneously the modified starch aqueous solution after the deoxygenation is sent in the same hypergravity RPB emulsator with 30.9Kg/ hour flow, obtained the vitamin A emulsion from outlet.
The continuous atomizing of said vitamin A emulsion is sprayed into pelletize in the cooled starch bed, after 20 hours, obtain the wet type vitamin A microcapsules of about 1100Kg.
Above-mentioned wet type vitamin A microcapsules is forwarded in the fluid bed, carry out fluidized drying and gelation processing, obtain the 548Kg type vitamin A microcapsules at last with 75 ℃ of hot nitrogens.Analyze through HPLC, wherein the content of vitamin A is 36.05%, and the micro encapsulation yield is 98.78%.Behind the storage at normal temperature 2 years, content is 34.72%, and the vitamin A retention rate is 96.3%.
Embodiment 3
Under nitrogen protection, the vitamin A crystallization was added in the special watery fusion device with 0.05Kg/ hour with 0.05Kg/ hour, BHA with 10Kg/ hour, antioxidant BHT, make watery fusion in 75 ℃, obtain 10.1Kg/ hour vitamin A melting oil.
But gelation modified starch 424.2Kg is dissolved in the 787.8Kg70 ℃ of water, is made into 35% modified starch aqueous solution, and in-0.075MPa the degassing 1.5 hours.
The molten oil of said vitamin A sent into 10.1Kg/ hour flow with pump to have liquid distribution trough, rotating speed be in 2000 rev/mins the hypergravity RPB emulsator, simultaneously the modified starch aqueous solution after the deoxygenation is sent in the same hypergravity RPB emulsator with 60.6Kg/ hour flow, obtained the vitamin A emulsion from outlet.
The continuous atomizing of said vitamin A emulsion is sprayed into pelletize in the cooled starch bed, after 20 hours, obtain the wet type vitamin A microcapsules of about 1800Kg.
Above-mentioned wet type vitamin A microcapsules is forwarded in the fluid bed, carry out fluidized drying and gelation processing, obtain the 776Kg type vitamin A microcapsules at last with 70 ℃ of hot nitrogens.Analyze through HPLC, wherein the content of vitamin A is 25.53%, and the micro encapsulation yield is 99.06%.Behind the storage at normal temperature 2 years, content is 24.69%, and the vitamin A retention rate is 96.7%.
Comparative example 1
In the molten oily still of the crystallization of 200Kg vitamin A, 10Kg ethoxy quinoline input, make watery fusion in 65 ℃, obtain 210Kg vitamin A melting oil.
Common modified starch 567Kg and 260Kg dextrin are dissolved in the 1930Kg65 ℃ of water, are made into 30% modified starch aqueous solution.
Above-mentioned modified starch aqueous solution input is equipped with in the emulsifying still of high speed shear mulser, under high speed shear, the molten oil of said vitamin A is added in the emulsifying still, finish re-shearing emulsifying 1 hour.Then under shearing condition at a slow speed, above-mentioned emulsion is carried out spray drying with 300Kg/ hour flow, sprayed after 9.9 hours.Obtain the 1006Kg type vitamin A microcapsules at last.Analyze through HPLC, wherein contain retinol1 8.86%, the micro encapsulation yield is 94.89%.Behind the storage at normal temperature 2 years, content is 17.07%, and the vitamin A retention rate is 90.5%.
Comparative example 2
In the molten oily still of the crystallization of 200Kg vitamin A, 6Kg tocopherol input, make watery fusion in 70 ℃, obtain 206Kg vitamin A melting oil.
Common modified starch 247.2Kg and 115Kg dextrin are dissolved in the 543Kg75 ℃ of water, are made into 40% modified starch aqueous solution.
Above-mentioned modified starch aqueous solution input is equipped with in the emulsifying still of high speed shear mulser, under high speed shear, the molten oil of said vitamin A is added in the emulsifying still, finish re-shearing emulsifying 1 hour.Then under shearing condition at a slow speed, above-mentioned emulsion is carried out spray drying with 300Kg/ hour flow, sprayed after 3.7 hours.Obtain the 550Kg type vitamin A microcapsules at last.Analyze through HPLC, wherein contain 3-Hydroxyretinol 4.62%, the micro encapsulation yield is 95.20%.Behind the storage at normal temperature 2 years, content is 30.88%, and the vitamin A retention rate is 89.2%.
Comparative example 3
The crystallization of 200Kg vitamin A, 1KgBHT and 1KgBHA are dropped in the molten oily still, make watery fusion in 75 ℃, obtain 202Kg vitamin A melting oil.
Common modified starch 424.2Kg and 180Kg dextrin are dissolved in the 1122Kg70 ℃ of water, are made into 35% modified starch aqueous solution.
Above-mentioned modified starch aqueous solution input is equipped with in the emulsifying still of high speed shear mulser, under high speed shear, the molten oil of said vitamin A is added in the emulsifying still, finish re-shearing emulsifying 1 hour.Then under shearing condition at a slow speed, above-mentioned emulsion is carried out spray drying with 300Kg/ hour flow, sprayed after 6.4 hours.Obtain the 780Kg type vitamin A microcapsules at last.Analyze through HPLC, wherein contain dehydroretinol 4.49%, the micro encapsulation yield is 95.52%.Behind the storage at normal temperature 2 years, content is 22.24%, and the vitamin A retention rate is 90.8%.

Claims (3)

1. the preparation method of a stable-type vitamin A microcapsules continuously is characterized in that may further comprise the steps:
1) under nitrogen protection, vitamin A crystallization, antioxidant are added in the watery fusion device continuously by 100: 1~5 part by weight, in 65~75 ℃ of fusings, be made into the vitamin A melting oil that contains antioxidant;
2) but the gelation modified starch is dissolved in 65~75 ℃ of water, be made into 30~40% modified starch aqueous solutions, and in-0.07~-the 0.08MPa vacuum under deoxygenation 1~2 hour;
3) vitamin A melting is oily with being pumped in the hypergravity RPB emulsator that has liquid distribution trough; Simultaneously, the modified starch aqueous solution after the deoxygenation with being pumped in the same hypergravity RPB emulsator, is obtained the vitamin A emulsion in outlet, vitamin A melting oil is 1: 3~9 with the weight ratio of modified starch aqueous solution;
4) with the vitamin A emulsion continuously atomizing spray into and carry out pelletize in the cooled starch bed, then with nitrogen as the fluid bed of drying medium in 65~75 ℃ carry out fluidized drying, gelation is handled, and promptly obtains stable-type vitamin A microcapsules.
2. the preparation method of a kind of stable-type vitamin A microcapsules continuously according to claim 1 is characterized in that described antioxidant is ethoxy quinoline, tocopherol, BHT or BHA.
3. the preparation method of a kind of stable-type vitamin A microcapsules continuously according to claim 1 is characterized in that described hypergravity RPB emulsator has liquid distribution trough, and filler is a metal gauze, and rotating speed is 1500~2500 rev/mins.
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Cited By (9)

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CN102224934A (en) * 2011-05-30 2011-10-26 何德海 Preparation method of vitamin A microcapsule nutrition enhancer for beverage
WO2012129765A1 (en) * 2011-03-25 2012-10-04 浙江新和成股份有限公司 Method for preparing stable-type vitamin a microcapsules continuously
CN104351473A (en) * 2014-10-22 2015-02-18 浙江万方生物科技有限公司 Preparation method of water-soluble multivitamin micropills for livestock and poultry
WO2019024548A1 (en) 2017-07-31 2019-02-07 浙江新和成股份有限公司 Fat-soluble nutrient microcapsule and preparation method therefor
CN109418541A (en) * 2017-09-01 2019-03-05 浙江医药股份有限公司新昌制药厂 A kind of preparation method of novel hydrophobic type liposoluble vitamin microcapsules
CN113785987A (en) * 2021-09-14 2021-12-14 万华化学集团股份有限公司 Preparation method of vitamin A microcapsule
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CN114586984A (en) * 2020-12-07 2022-06-07 万华化学集团股份有限公司 Method for continuously preparing vitamin A microcapsules
CN115381104A (en) * 2022-08-10 2022-11-25 新昌新和成维生素有限公司 Preparation method and device of vitamin A microcapsules

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CN1965657A (en) * 2006-11-27 2007-05-23 江南大学 Method for preparing flour nutrition intensifying Vitamin A microcapsule
CN101574632B (en) * 2008-05-09 2011-07-13 北京化工大学 Preparation method of cod-liver oil emulsion
CN101513394B (en) * 2009-03-30 2011-04-27 浙江新和成股份有限公司 Continuous preparation method for nanometer dispersed vitamin A microcapsule

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WO2012129765A1 (en) * 2011-03-25 2012-10-04 浙江新和成股份有限公司 Method for preparing stable-type vitamin a microcapsules continuously
US9173818B2 (en) 2011-03-25 2015-11-03 Zhejiang Nhu Company Ltd Method for preparing stable-type vitamin A microcapsules continuously
CN102224934B (en) * 2011-05-30 2013-09-18 何德海 Preparation method of vitamin A microcapsule nutrition enhancer for beverage
CN102224934A (en) * 2011-05-30 2011-10-26 何德海 Preparation method of vitamin A microcapsule nutrition enhancer for beverage
CN104351473A (en) * 2014-10-22 2015-02-18 浙江万方生物科技有限公司 Preparation method of water-soluble multivitamin micropills for livestock and poultry
CN104351473B (en) * 2014-10-22 2018-02-02 刘希悦 A kind of preparation method of Aquavite micropill for livestock and poultry
WO2019024548A1 (en) 2017-07-31 2019-02-07 浙江新和成股份有限公司 Fat-soluble nutrient microcapsule and preparation method therefor
CN109418541B (en) * 2017-09-01 2022-08-19 浙江医药股份有限公司新昌制药厂 Preparation method of hydrophobic fat-soluble vitamin microcapsule
CN109418541A (en) * 2017-09-01 2019-03-05 浙江医药股份有限公司新昌制药厂 A kind of preparation method of novel hydrophobic type liposoluble vitamin microcapsules
CN114586984B (en) * 2020-12-07 2023-12-19 万华化学集团股份有限公司 Method for continuously preparing vitamin A microcapsules
CN114586984A (en) * 2020-12-07 2022-06-07 万华化学集团股份有限公司 Method for continuously preparing vitamin A microcapsules
CN113785987A (en) * 2021-09-14 2021-12-14 万华化学集团股份有限公司 Preparation method of vitamin A microcapsule
CN114315675A (en) * 2022-01-05 2022-04-12 万华化学集团股份有限公司 Preparation of hot water insoluble vitamin A acetate particles
CN114315675B (en) * 2022-01-05 2024-02-02 万华化学集团股份有限公司 Preparation of hot water insoluble vitamin A acetate particles
CN115381104A (en) * 2022-08-10 2022-11-25 新昌新和成维生素有限公司 Preparation method and device of vitamin A microcapsules
CN115381104B (en) * 2022-08-10 2024-04-02 新昌新和成维生素有限公司 Preparation method and device of vitamin A microcapsule

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