CN111233813A - Method for removing glycidyl ester in mixed tocopherol - Google Patents
Method for removing glycidyl ester in mixed tocopherol Download PDFInfo
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- CN111233813A CN111233813A CN202010147931.XA CN202010147931A CN111233813A CN 111233813 A CN111233813 A CN 111233813A CN 202010147931 A CN202010147931 A CN 202010147931A CN 111233813 A CN111233813 A CN 111233813A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
- C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
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Abstract
A method for removing glycidyl esters from mixed tocopherols, comprising the steps of: (A) saponifying 50% of natural VE product with 5% of sodium hydroxide ethanol solution, (B) adding petroleum ether for extraction, (C) adsorbing collected oil phase by a column, and adsorbing by first-stage strong base ion exchange resin to remove acidic impurities; (D) adsorbing the collected liquid with column, adsorbing VE with second stage strong base ion exchange resin, washing the bed layer with anhydrous ethanol to remove non-adsorbed substances, and (E) adsorbing with CO2Desorbing VE to obtain natural VE mixed tocopherol; (F) the short-path distillation vacuum degree is controlled to be less than or equal to 1Pa, the temperature is controlled to be less than or equal to 195 ℃, the generation of glycidyl ester is reduced at low temperature, the content of VE mixed tocopherol glycidyl ester with the purity of more than 95 percent obtained by refining is low, and the content of VE mixed tocopherol glycidyl ester is 110ppb and less by SGS detection and is far lower than the European Union limit value of 1000 ppb.
Description
Technical Field
The invention relates to the technical field of natural food additive production, in particular to a method for removing glycidyl ester in mixed tocopherol.
Background
A series of natural vitamin E (VE for short) is prepared from deodorized edible vegetable oil (DD oil) containing 6% VE through preparing mixed tocopherol (50%) and then 90%, further processing d- α, d- α, D- α and succinic acid.
Vitamin E has important physiological functions, is a nutrient essential for human and animals, and is widely applied to industries of medicines, health products, beauty and skin care products, food, feed additives and the like. At present, the vitamin E is the vitamin variety with the fastest increase of the demand and the sales volume in the international market, and compared with the synthetic VE, the natural VE is favored by people due to the characteristics of high activity, pure nature, safety, reliability and the like. The natural VE industry of western countries starts earlier, and at present, the manufacturing technology and the product technology level are ahead of domestic enterprises, but due to the restriction of raw material resources (edible vegetable oil deodorized distillate), the increase of the yield of countries such as Europe and America cannot meet the increase of demand, and the market gap needs to be made up through import, but the requirements of the countries such as Europe and America on natural VE are very strict, and the requirements on the content, purity, trace impurities and the like have strict quality index requirements.
In the oil and fat refining process, glycidyl ester is usually formed along with 3-chloropropanol ester, the 3-chloropropanol ester content is high, and the glycidyl ester content is also high. 3-chloropropanol esters and glycidyl esters have become a new class of contaminants of global interest in vegetable oils. Since the export country of the company is mainly the European and American countries, the technical trade barrier set by the European Union must be broken through to develop a method for removing glycidyl ester from 90% mixed tocopherol.
Disclosure of Invention
The invention aims to solve the technical problem that glycidyl ester in mixed tocopherol is removed, and the obtained product can meet the requirements of European union countries on the quality index of the glycidyl ester.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the method comprises the steps of firstly saponifying and then acidifying a natural mixed tocopherol product with the content of 50% produced by a company, then adding petroleum ether for extraction, washing with hot water to remove glycidol, alkali and the like, adsorbing a collected oil phase on a column, and adsorbing by using two-stage strong base ion exchange resin to finally obtain the natural VE mixed tocopherol with the content of more than 95%, wherein the content of glycidyl ester is far lower than the European union limit value of 1000 ppb.
A method for removing glycidyl esters from mixed tocopherols, comprising the steps of:
(A) saponifying 50% natural VE product with 5% sodium hydroxide ethanol solution, wherein the amount of the 5% sodium hydroxide ethanol solution is 28-32% of that of the 50% natural VE product, and acidifying with sulfuric acid, wherein the amount of the concentrated sulfuric acid is 1.8-2.2% of that of the raw material;
(B) extracting with petroleum ether 2-3 times of the raw materials at 68-72 deg.C
Washing with hot water to remove glycidol, salts, excess acid, etc.;
(C) adsorbing the collected oil phase by a column, and adsorbing by first-stage strong base ion exchange resin to remove acidic impurities;
(D) adsorbing the collected liquid by a column, adsorbing VE by second-stage strong base ion exchange resin, washing a bed layer by absolute ethyl alcohol to remove non-adsorbed substances, wherein the amount of the absolute ethyl alcohol is 2.5-3.5 times of the volume of the column;
(E) with CO2Desorbing VE to obtain natural VE mixed tocopherol;
(F) controlling the vacuum degree of short-path distillation to be less than or equal to 1Pa and the temperature to be less than or equal to 195 ℃, controlling the low temperature to reduce the generation of glycidyl ester, and refining to obtain more than 95 percent of VE mixed tocopherol.
According to the method for removing glycidyl ester in mixed tocopherol, the VE content of the obtained VE mixed tocopherol product is 95% or more, wherein the content of the glycidyl ester is low, and is 110ppb or less by SGS detection and far lower than the European Union limit value of 1000 ppb.
Detailed Description
The present invention will be further described with reference to the following examples, which are provided only for illustrating the present invention and are not intended to limit the present invention.
The method comprises the steps of firstly saponifying and then acidifying a natural mixed tocopherol product with the content of 50% produced by a company, then adding petroleum ether for extraction, washing with hot water to remove glycidol, alkali and the like, adsorbing a collected oil phase on a column, and adsorbing by using two-stage strong base ion exchange resin to finally obtain the natural VE mixed tocopherol with the content of more than 95%, wherein the content of glycidyl ester is far lower than the European union limit value of 1000 ppb.
Example one
A method for removing glycidyl esters from mixed tocopherols, comprising the steps of:
(A) saponifying 50% of natural VE product with 5% of sodium hydroxide ethanol solution, wherein the amount of the 5% of sodium hydroxide ethanol solution is 30% of the amount of the 50% of the natural VE product, and acidifying with sulfuric acid, wherein the amount of concentrated sulfuric acid is 2% of the amount of the raw material;
(B) adding petroleum ether for extraction, wherein the amount of the petroleum ether is 2.5 times of that of the raw material, washing the extract with hot water at 70 ℃ to remove glycidol, salt, excessive acid and the like;
(C) adsorbing the collected oil phase by a column, and adsorbing by first-stage strong base ion exchange resin to remove acidic impurities;
(D) the collected liquid is subjected to column adsorption, the second-stage strong base ion exchange resin adsorbs VE, and the bed layer is washed by absolute ethyl alcohol to remove non-adsorbed substances, wherein the amount of the absolute ethyl alcohol is 3 times of the volume of the column;
(E) with CO2Desorbing VE to obtain natural VE mixed tocopherol;
(F) controlling the vacuum degree of short-path distillation to be less than or equal to 1Pa and the temperature to be less than or equal to 195 ℃, controlling the low temperature to reduce the generation of glycidyl ester, and refining to obtain more than 95 percent of VE mixed tocopherol.
According to the method for removing glycidyl ester in mixed tocopherol, the VE content of the obtained VE mixed tocopherol product is 95.2%, wherein the content of the glycidyl ester is low, and the content of the glycidyl ester is far lower than the European Union limit value of 1000ppb through SGS detection.
Example two
A method for removing glycidyl esters from mixed tocopherols, comprising the steps of:
(A) saponifying 50% of natural VE product with 5% of sodium hydroxide ethanol solution, wherein the amount of the 5% of sodium hydroxide ethanol solution is 28% of the amount of the 50% of the natural VE product, and acidifying with sulfuric acid, wherein the amount of concentrated sulfuric acid is 2.2% of the amount of the raw material;
(B) adding petroleum ether for extraction, wherein the amount of the petroleum ether is 2 times of that of the raw materials, washing the extract with hot water at 68 ℃ to remove glycidol, salt, excessive acid and the like;
(C) adsorbing the collected oil phase by a column, and adsorbing by first-stage strong base ion exchange resin to remove acidic impurities;
(D) the collected liquid is subjected to column adsorption, the second-stage strong base ion exchange resin adsorbs VE, and the bed layer is washed by absolute ethyl alcohol to remove non-adsorbed substances, wherein the amount of the absolute ethyl alcohol is 3.5 times of the volume of the column;
(E) with CO2Desorbing VE to obtain natural VE mixed tocopherol;
(F) controlling the vacuum degree of short-path distillation to be less than or equal to 1Pa and the temperature to be less than or equal to 195 ℃, controlling the low temperature to reduce the generation of glycidyl ester, and refining to obtain more than 95 percent of VE mixed tocopherol.
According to the method for removing glycidyl ester in mixed tocopherol, the VE content of the obtained VE mixed tocopherol product is 95.1%, wherein the content of the glycidyl ester is low, and 108ppb is detected by SGS and is far lower than the European Union limit value of 1000 ppb.
EXAMPLE III
A method for removing glycidyl esters from mixed tocopherols, comprising the steps of:
(A) saponifying 50% of natural VE product with 5% of sodium hydroxide ethanol solution, wherein the amount of the 5% of sodium hydroxide ethanol solution is 32% of the amount of the 50% of the natural VE product, and acidifying with sulfuric acid, wherein the amount of concentrated sulfuric acid is 1.8% of the amount of the raw material;
(B) adding petroleum ether for extraction, wherein the amount of the petroleum ether is 3 times of that of the raw materials, washing the extract with hot water at 72 ℃ to remove glycidol, salt, excessive acid and the like;
(C) adsorbing the collected oil phase by a column, and adsorbing by first-stage strong base ion exchange resin to remove acidic impurities;
(D) the collected liquid is subjected to column adsorption, the second-stage strong base ion exchange resin adsorbs VE, and the bed layer is washed by absolute ethyl alcohol to remove non-adsorbed substances, wherein the amount of the absolute ethyl alcohol is 2.5 times of the volume of the column;
(E) with CO2Desorbing VE to obtain natural VE mixed tocopherol;
(F) controlling the vacuum degree of short-path distillation to be less than or equal to 1Pa and the temperature to be less than or equal to 195 ℃, controlling the low temperature to reduce the generation of glycidyl ester, and refining to obtain more than 95 percent of VE mixed tocopherol.
According to the method for removing glycidyl ester in mixed tocopherol, the VE content of the obtained VE mixed tocopherol product is 95.2%, wherein the content of the glycidyl ester is low, 109ppb is detected by SGS, and is far lower than the European Union limit value of 1000 ppb.
Claims (1)
1. A method for removing glycidyl esters from mixed tocopherols, comprising the steps of:
(A) saponifying 50% natural VE product with 5% sodium hydroxide ethanol solution, wherein the amount of the 5% sodium hydroxide ethanol solution is 28-32% of that of the 50% natural VE product, and acidifying with sulfuric acid, wherein the amount of the concentrated sulfuric acid is 1.8-2.2% of that of the raw material;
(B) adding petroleum ether for extraction, wherein the amount of petroleum ether is 2-3 times of the raw material amount, washing the extract with hot water of 68-72 deg.C, and removing glycidol, salt and excessive acid;
(C) adsorbing the collected oil phase by a column, and adsorbing by first-stage strong base ion exchange resin to remove acidic impurities;
(D) adsorbing the collected liquid by a column, adsorbing VE by second-stage strong base ion exchange resin, washing a bed layer by absolute ethyl alcohol to remove non-adsorbed substances, wherein the amount of the absolute ethyl alcohol is 2.5-3.5 times of the volume of the column;
(E) with CO2Desorbing VE to obtain natural VE mixed tocopherol;
(F) controlling the vacuum degree of short-path distillation to be less than or equal to 1Pa and the temperature to be less than or equal to 195 ℃, controlling the low temperature to reduce the generation of glycidyl ester, and refining to obtain more than 95 percent of VE mixed tocopherol.
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| CN202010147931.XA CN111233813A (en) | 2020-03-05 | 2020-03-05 | Method for removing glycidyl ester in mixed tocopherol |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584769A (en) * | 2011-12-20 | 2012-07-18 | 浙江华源制药科技开发有限公司 | Preparation method of natural VE with content of more than 99% |
| EP2641473A1 (en) * | 2012-03-20 | 2013-09-25 | Cargill Inc. | High oleic palm oil fractions |
| CN103588744A (en) * | 2013-10-31 | 2014-02-19 | 宁波大红鹰生物工程股份有限公司 | Method for removing plasticizer from natural vitamin E |
| CN103709133A (en) * | 2013-12-27 | 2014-04-09 | 合肥工业大学 | Method for purifying tocopherol from deodorized distillate of vegetable oil based on weak acid condition |
| CN104130233A (en) * | 2014-07-03 | 2014-11-05 | 山东圣地嘉禾生物工程有限公司 | Method for preparing natural alpha tocopherol and mixing tocopherol by one-step method |
| CN105693683A (en) * | 2014-11-28 | 2016-06-22 | 丰益(上海)生物技术研发中心有限公司 | A method of removing a plasticiser from vitamin E |
| CN108753458A (en) * | 2018-08-03 | 2018-11-06 | 梁云 | Improve the refinery practice of microbial grease stability and safety |
| CN110257169A (en) * | 2019-06-12 | 2019-09-20 | 深圳精益油脂技术有限公司 | A method of preparing the palm oil of low ethylene oxidic ester and low 3-MCPD ester content |
-
2020
- 2020-03-05 CN CN202010147931.XA patent/CN111233813A/en not_active Withdrawn
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584769A (en) * | 2011-12-20 | 2012-07-18 | 浙江华源制药科技开发有限公司 | Preparation method of natural VE with content of more than 99% |
| EP2641473A1 (en) * | 2012-03-20 | 2013-09-25 | Cargill Inc. | High oleic palm oil fractions |
| CN103588744A (en) * | 2013-10-31 | 2014-02-19 | 宁波大红鹰生物工程股份有限公司 | Method for removing plasticizer from natural vitamin E |
| CN103709133A (en) * | 2013-12-27 | 2014-04-09 | 合肥工业大学 | Method for purifying tocopherol from deodorized distillate of vegetable oil based on weak acid condition |
| CN104130233A (en) * | 2014-07-03 | 2014-11-05 | 山东圣地嘉禾生物工程有限公司 | Method for preparing natural alpha tocopherol and mixing tocopherol by one-step method |
| CN105693683A (en) * | 2014-11-28 | 2016-06-22 | 丰益(上海)生物技术研发中心有限公司 | A method of removing a plasticiser from vitamin E |
| CN108753458A (en) * | 2018-08-03 | 2018-11-06 | 梁云 | Improve the refinery practice of microbial grease stability and safety |
| CN110257169A (en) * | 2019-06-12 | 2019-09-20 | 深圳精益油脂技术有限公司 | A method of preparing the palm oil of low ethylene oxidic ester and low 3-MCPD ester content |
Non-Patent Citations (2)
| Title |
|---|
| 姜洪峰等: "菜籽油脱臭馏出物中天然V_E和植物甾醇提取工艺研究", 《中国粮油学报》 * |
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