CN107954969B

CN107954969B - Extraction process of high-quality vitamin E

Info

Publication number: CN107954969B
Application number: CN201711225051.4A
Authority: CN
Inventors: 徐小毛
Original assignee: Luomai Beijing Nutritional Food Research Co ltd
Current assignee: Guanwei Intelligent Technology (Beijing) Co.,Ltd.
Priority date: 2017-11-29
Filing date: 2017-11-29
Publication date: 2021-07-23
Anticipated expiration: 2037-11-29
Also published as: CN107954969A

Abstract

The invention discloses an extraction process of high-quality vitamin E, which comprises the following steps: (1) removing water in the grease deodorized distillate; (2) esterifying free fatty acid in the grease deodorized distillate; (3) removing the sterol; (4) removing fatty acid methyl ester. The extraction process of high-quality vitamin E has simple, convenient and feasible process and high extraction efficiency, and the obtained vitamin E can be widely used as a nutritional supplement and an antioxidant in the pharmaceutical, cosmetic and food industries.

Description

Extraction process of high-quality vitamin E

Technical Field

The invention relates to the technical field of vitamin E preparation, in particular to a high-quality vitamin E extraction process.

Background

Vitamin E is an essential vitamin for the human body and is one of bioactive substances essential to living organisms. With the development of nutrition and pathology, a series of biochemical functions of vitamin E are continuously discovered and confirmed. Therefore, research, development and utilization of vitamin E are still underway.

Vitamin E, also known as anti-infertility vitamin, is one of the first vitamins found by people. Vitamin E is a generic term for a group of derivatives that are chemically related to tocopherols, tocotrienols and other derivatives that exhibit more or less d-alpha-tocopherol bioactivity. The vitamin E is generally nontoxic, and animal experiments such as rats show that the vitamin E is safe to eat, and even if the intake dose is far higher than a normal value, the side effect is difficult to find. Vitamin E usually accumulates in the subcutaneous fat and liver, which have a high storage capacity, and when it is excessive, it becomes tocopherol lactone, which is excreted in urine, or it is excreted together with sweat through the sebaceous glands. Vitamin E is absorbed into blood from lymphatic capillaries in the upper part of small intestine in the form of chylomicron, and is carried and transported to various tissues and organs in vivo by lipoprotein, and the content of vitamin E is the most in brain tissues and adrenal glands. It is distributed in the cell mainly in microsomes and mitochondria.

Vitamin E is found primarily in a variety of plant materials, with comparable levels in oilseeds, certain cereals, nuts, and green vegetables. The content of the animal tissue is extremely low. With the increasing understanding and application of vitamin E in international and domestic fields, the demand of vitamin E in the international market is increasing. Those in the trade indicate that: vitamin E sales are increasing in the world market at a rate of 12% -15% of the year. Therefore, the problem that how to utilize the huge resource of deodorized distillate in China to extract vitamin E in rapeseed deodorized distillate and research on physiological functions of the deodorized distillate to generate natural vitamin E products is urgently needed to be solved by people is solved.

Disclosure of Invention

The invention aims to solve the technical problem of providing a production method of vitamin E.

The invention provides an extraction process of high-quality vitamin E, which comprises the following steps:

(1) removing water in the grease deodorized distillate;

(2) esterifying free fatty acid in the grease deodorized distillate;

(3) removing the sterol;

(4) removing fatty acid methyl ester.

Specifically, the extraction process of the high-quality vitamin E comprises the following steps:

(1) removing water in the grease deodorized distillate: treating the grease deodorization distillate for 30-40 minutes by adopting a wiped film evaporator under the conditions of the temperature of 100-;

(2) esterifying free fatty acid in the grease deodorized distillate: converting free fatty acid in the grease deodorized distillate into free fatty acid methyl ester to obtain an esterification product;

(3) removing sterol: placing the esterification product at 5-10 ℃ for 16-24 hours, then filtering by adopting 300-mesh filter cloth with 500 meshes, and collecting filtrate;

(4) removing fatty acid methyl ester: and (3) performing molecular distillation on the filtrate by adopting a wiped film type molecular distiller, wherein the primary distillation temperature is 110-.

(3) transesterification of glycerides: weighing an esterification product into a reaction vessel, adding methanol and sodium methoxide, wherein the volume mass ratio of the methanol to the esterification product is (0.7-1): 1(mL/g), wherein the weight of sodium methoxide is 0.05-0.06% of the weight of an esterification product, the components are uniformly mixed, the mixture is stirred and reacted for 1-3 hours at the temperature of 65-75 ℃ and the rotating speed of 100 rpm, after the reaction is finished, hydrochloric acid aqueous solution with the mass fraction of 5-10% is added, and the weight ratio of the hydrochloric acid aqueous solution to the sodium methoxide is (0.8-0.9): 1, mixing, layering the mixed solution in a separating funnel, taking supernatant, washing the supernatant with water at 65-75 ℃, wherein the mass ratio of the supernatant to the washing water is 1: (5-10), adding anhydrous sodium sulfate which is 0.2-0.3 time of the weight of the supernatant into the washed supernatant, standing for 10-20 minutes, filtering by using 300-plus 500-mesh filter cloth, and drying the filtrate for 1-2 hours under the conditions that the vacuum degree is 0.06-0.07MPa and the temperature is 50-60 ℃ to obtain a transesterification product;

(4) removing sterol: placing the transesterification product at 5-10 ℃ for 16-24 hours, then filtering by adopting 300-mesh filter cloth with 500 meshes, and collecting filtrate;

(5) removing fatty acid methyl ester: and (3) performing molecular distillation on the filtrate by adopting a wiped film type molecular distiller, wherein the primary distillation temperature is 110-.

In some embodiments of the present invention, the specific process of esterifying the free fatty acids in the grease deodorized distillate in step (2) is: weighing the grease deodorized distillate, placing the grease deodorized distillate into a reactor, adding methanol and 75-98% sulfuric acid water solution by mass, wherein the volume mass ratio of the methanol to the grease deodorized distillate is (1.3-1.5): 1(mL/g), the weight of the sulfuric acid aqueous solution is 0.03-0.04% of the weight of the grease deodorized distillate, the components are uniformly mixed, the mixture is stirred and reacted for 2-4 hours at the temperature of 60-70 ℃ at the rotating speed of 100 rpm, the reaction solution is placed in a separating funnel for layering, the upper layer solution is taken, the upper layer solution is washed by water at the temperature of 60-70 ℃, and the mass ratio of the upper layer solution to the washing water is 1: (5-10), adding anhydrous sodium sulfate with the weight 0.2-0.3 time of that of the supernatant into the washed supernatant, standing for 10-20 minutes, filtering by using 300-mesh filter cloth with 500 meshes, and drying the filtrate for 1-2 hours under the conditions of the vacuum degree of 0.06-0.07MPa and the temperature of 50-60 ℃ to obtain an esterification product.

In some embodiments of the present invention, the specific process of esterifying the free fatty acids in the grease deodorized distillate in step (2) is: the method comprises the steps of adopting a strong-acid cation exchange resin as a catalyst, filling the strong-acid cation exchange resin into a reaction column of a fixed bed, mixing methanol and grease deodorized distillate to prepare a reaction solution, wherein the weight ratio of the methanol to the grease deodorized distillate is (1.5-2.5): 1, introducing a reaction solution into a reaction column from bottom to top by using a metering pump, wherein the temperature of the reaction column is 50-60 ℃, the flow rate is 1.57-4.18 mL/min, the contact time is 1-2 hours, placing the reaction solution into a separating funnel for layering, taking an upper layer solution, washing the upper layer solution by using water at the temperature of 50-60 ℃, and the mass ratio of the upper layer solution to washing water is 1: (5-10), adding anhydrous sodium sulfate with the weight 0.2-0.3 time of that of the supernatant into the washed supernatant, standing for 10-20 minutes, filtering by using 300-mesh filter cloth with 500 meshes, and drying the filtrate for 1-2 hours under the conditions of the vacuum degree of 0.06-0.07MPa and the temperature of 50-60 ℃ to obtain an esterification product.

In some embodiments of the present invention, the specific process of esterifying the free fatty acids in the grease deodorized distillate in step (2) is: weighing the grease deodorized distillate, placing the grease deodorized distillate into a reactor, adding methanol and lipase, wherein the volume mass ratio of the methanol to the grease deodorized distillate is (0.25-0.35): 1(mL/g), adding 60-80plu/g of grease deodorized distillate into lipase, uniformly mixing, stirring and reacting for 3-8 hours at 50-60 ℃ at the rotation speed of 100-: (5-10), adding anhydrous sodium sulfate with the weight 0.2-0.3 time of that of the supernatant into the washed supernatant, standing for 10-20 minutes, filtering by using 300-mesh filter cloth with 500 meshes, and drying the filtrate for 1-2 hours under the conditions of the vacuum degree of 0.06-0.07MPa and the temperature of 50-60 ℃ to obtain an esterification product.

In some embodiments of the present invention, the esterification of the free fatty acid in the grease deodorized distillate in step (2) is performed in two steps, specifically: weighing the grease deodorized distillate, placing the grease deodorized distillate into a reactor, adding methanol and lipase, wherein the volume mass ratio of the methanol to the grease deodorized distillate is (0.25-0.35): 1(mL/g), adding 60-80plu/g of grease deodorized distillate into lipase, uniformly mixing, stirring and reacting at 50-60 ℃ for 3-8 hours at a rotation speed of 100-; then, using a strong acid cation exchange resin as a catalyst, filling the strong acid cation exchange resin into a reaction column of a fixed bed, mixing methanol and a primary esterification product to prepare a reaction solution, wherein the mass ratio of the methanol to the primary esterification product is (1.5-2.5): 1, introducing a reaction solution into a reaction column from bottom to top by using a metering pump, wherein the temperature of the reaction column is 50-60 ℃, the flow rate is 1.57-4.18 mL/min, the contact time is 1-2 hours, placing the reaction solution into a separating funnel for layering, taking an upper layer solution, washing the upper layer solution by using water at the temperature of 50-60 ℃, and the mass ratio of the upper layer solution to washing water is 1: (5-10), adding anhydrous sodium sulfate with the weight 0.2-0.3 time of that of the supernatant into the washed supernatant, standing for 10-20 minutes, filtering by using 300-mesh filter cloth with 500 meshes, and drying the filtrate for 1-2 hours under the conditions of the vacuum degree of 0.06-0.07MPa and the temperature of 50-60 ℃ to obtain a secondary esterification product.

The lipase is selected from one or more of a Mucor miehei immobilized enzyme, a Chiralzyme IM-100 immobilized enzyme and a Novozym435 immobilized enzyme. Preferably, the lipase is a mixture of Chiralzyme IM-100 immobilized enzyme and Novozym435 immobilized enzyme, wherein the weight ratio of the Chiralzyme IM-100 immobilized enzyme to the Novozym435 immobilized enzyme is 1: (1.5-2).

The grease deodorized distillate can be soybean oil deodorized distillate, rapeseed oil deodorized distillate, peanut oil deodorized distillate or palm oil deodorized distillate.

The extraction process of high-quality vitamin E has simple, convenient and feasible process and high extraction efficiency, and the obtained vitamin E can be widely used as a nutritional supplement and an antioxidant in the pharmaceutical, cosmetic and food industries.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

In the embodiment described below, it is preferred that,

the soybean oil deodorized distillate was purchased from grain oil of east China sea (Zhang hong) Ltd.

The wiped film evaporator is purchased from Hangzhou mechanical equipment, Inc. of LG-8.

A wiped film molecular distiller, model FMD-100, was purchased from Shanghai Dafeng glass instruments, Inc.

Novozym435 immobilized enzyme, purchased from Novovin, Denmark, and having an enzyme activity of 10000 plu/g. A strong acid cation exchange resin, available from Shanghai Kaiping resin Co., Ltd, type D001.

The methanol is anhydrous methanol provided by Shanghai Kangshi chemical science and technology Limited.

The fixed bed reactor is purchased from Toxico lake Longhu petrochemical equipment Co., Ltd, and has model number of LHSH-018, the inner diameter of the bed layer of the fixed bed is 1.56cm, and the filling height of the resin is 88-96 cm.

Chiralzyme IM-100 immobilized enzyme, purchased from Denmark Novoxin, with an enzyme activity of 10000 plu/g.

Example 1

The extraction process of high-quality vitamin E comprises the following steps:

(1) treating the soybean oil deodorized distillate by a wiped film evaporator at the temperature of 110 ℃ and the vacuum degree of 0.1MPa for 40 minutes;

(2) weighing soybean oil deodorized distillate, placing the soybean oil deodorized distillate into a reactor, adding methanol and 98% sulfuric acid water solution in mass fraction, wherein the volume mass ratio of the methanol to the soybean oil deodorized distillate is 1.4: 1(mL/g), the weight of the sulfuric acid aqueous solution is 0.03 percent of the weight of the soybean oil deodorized distillate, the sulfuric acid aqueous solution and the soybean oil deodorized distillate are uniformly mixed, the mixture is stirred and reacted for 4 hours at the temperature of 60 ℃ at the rotating speed of 150 r/min, the reaction solution is placed in a separating funnel for layering, the upper layer solution is taken, the upper layer solution is washed by water at the temperature of 60 ℃, and the mass ratio of the upper layer solution to the washing water is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain an esterified product;

(3) standing the esterification product at 5 ℃ for 24 hours, then filtering by adopting 300-mesh filter cloth, and collecting filtrate;

(4) and (3) performing molecular distillation on the filtrate by adopting a wiped film type molecular distiller, wherein the primary distillation temperature is 110 ℃, the secondary distillation temperature is 150 ℃, the distillation pressure is 0.1Pa, the feeding rate is 90 mL/h, and the rotating speed of the wiped film distiller is 150 revolutions per minute to obtain the vitamin E.

Example 2

The extraction process of high-quality vitamin E comprises the following steps:

(3) weighing an esterification product into a reaction container, adding methanol and sodium methoxide, wherein the volume mass ratio of the methanol to the esterification product is 0.8: 1(mL/g), wherein the weight of sodium methoxide is 0.05 percent of the weight of an esterification product, the sodium methoxide and the esterification product are uniformly mixed, the mixture is stirred and reacted for 2 hours at the temperature of 70 ℃ at the rotating speed of 150 r/min, after the reaction is finished, a hydrochloric acid aqueous solution with the mass fraction of 5 percent is added, and the weight ratio of the hydrochloric acid aqueous solution to the sodium methoxide is 0.9: 1, layering the mixed solution in a separating funnel after mixing, taking supernatant, washing the supernatant with water at 70 ℃, wherein the mass ratio of the supernatant to the water for washing is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain a transesterification product;

(4) standing the transesterification product at 5 ℃ for 24 hours, filtering by adopting 300-mesh filter cloth, and collecting filtrate;

(5) and (3) performing molecular distillation on the filtrate by adopting a wiped film type molecular distiller, wherein the primary distillation temperature is 110 ℃, the secondary distillation temperature is 150 ℃, the distillation pressure is 0.1Pa, the feeding rate is 90 mL/h, and the rotating speed of the wiped film distiller is 150 revolutions per minute to obtain the vitamin E.

Example 3

The extraction process of high-quality vitamin E comprises the following steps:

(2) the method comprises the steps of adopting a strong-acid cation exchange resin as a catalyst, filling the strong-acid cation exchange resin into a reaction column of a fixed bed, mixing methanol and grease deodorized distillate to prepare a reaction solution, wherein the weight ratio of the methanol to the grease deodorized distillate is 2: 1, introducing a reaction solution into a reaction column from bottom to top by using a metering pump, wherein the temperature of the reaction column is 60 ℃, the flow rate is 1.57 mL/min, the contact time is 60 min, placing the reaction solution into a separating funnel for layering, taking supernatant, washing the supernatant by using water at the temperature of 60 ℃, and the mass ratio of the supernatant to water for washing is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain an esterified product;

Example 4

The extraction process of high-quality vitamin E comprises the following steps:

(2) weighing soybean oil deodorized distillate, putting the soybean oil deodorized distillate into a reactor, adding methanol and Novozym435 immobilized enzyme, wherein the volume mass ratio of the methanol to the soybean oil deodorized distillate is 0.3: 1(mL/g), adding 70plu/g soybean oil deodorized distillate of Novozym435 immobilized enzyme, uniformly mixing, stirring and reacting for 4 hours at the temperature of 60 ℃ at the rotating speed of 150 rpm, placing reaction liquid into a separating funnel for layering, taking upper layer liquid, washing the upper layer liquid with water at the temperature of 60 ℃, wherein the mass ratio of the upper layer liquid to the washing water is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain an esterified product;

(3) weighing an esterification product into a reaction container, adding methanol and sodium methoxide, wherein the volume mass ratio of the methanol to the esterification product is 0.8: 1(mL/g), wherein the weight of sodium methoxide is 0.05 percent of the weight of an esterification product, the sodium methoxide and the esterification product are uniformly mixed, the mixture is reacted at the temperature of 70 ℃ and stirred for 2 hours at the rotating speed of 150 r/min, after the reaction is finished, a hydrochloric acid aqueous solution with the mass fraction of 5 percent is added, and the weight ratio of the hydrochloric acid aqueous solution to the sodium methoxide is 0.9: 1, layering the mixed solution in a separating funnel after mixing, taking supernatant, washing the supernatant with water at 70 ℃, wherein the mass ratio of the supernatant to the water for washing is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain a transesterification product;

Example 5

The extraction process of high-quality vitamin E comprises the following steps:

(2) weighing soybean oil deodorized distillate, putting the soybean oil deodorized distillate into a reactor, adding methanol and Novozym435 immobilized enzyme, wherein the volume mass ratio of the methanol to the soybean oil deodorized distillate is 0.3: 1(mL/g), adding 70plu/g soybean oil deodorized distillate of Novozym435 immobilized enzyme, uniformly mixing, stirring and reacting at the temperature of 60 ℃ for 3 hours at the rotating speed of 150 rpm, placing the reaction liquid in a separating funnel for layering, taking the upper layer liquid, washing the upper layer liquid with water at the temperature of 60 ℃, wherein the mass ratio of the upper layer liquid to the washing water is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain a primary esterification product; the method comprises the following steps of adopting a strong-acid cation exchange resin as a catalyst, filling the strong-acid cation exchange resin into a reaction column of a fixed bed, mixing methanol and a primary esterification product to prepare a reaction solution, wherein the weight ratio of the methanol to the primary esterification product is 2: 1, introducing a reaction liquid into a reaction column from bottom to top by using a metering pump, wherein the temperature of the reaction column is 60 ℃, the flow rate is 1.57 mL/min, the contact time is 1 hour, placing the reaction liquid into a separating funnel for layering, taking supernatant liquid, washing the supernatant liquid by using water at the temperature of 60 ℃, and the mass ratio of the supernatant liquid to water for washing is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain a secondary esterification product;

(3) weighing a secondary esterification product into a reaction container, adding methanol and sodium methoxide, wherein the volume mass ratio of the methanol to the secondary esterification product is 0.8: 1(mL/g), wherein the weight of sodium methoxide is 0.05 percent of the weight of a secondary esterification product, the sodium methoxide and the secondary esterification product are uniformly mixed, the mixture is stirred and reacted for 2 hours at the temperature of 70 ℃ at the rotating speed of 150 r/min, after the reaction is finished, a hydrochloric acid aqueous solution with the mass fraction of 5 percent is added, and the weight ratio of the hydrochloric acid aqueous solution to the sodium methoxide is 0.9: 1, layering the mixed solution in a separating funnel after mixing, taking supernatant, washing the supernatant with water at 70 ℃, wherein the mass ratio of the supernatant to the water for washing is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain a transesterification product;

Example 6

The extraction process of high-quality vitamin E comprises the following steps:

(2) weighing soybean oil deodorized distillate, placing the soybean oil deodorized distillate into a reactor, adding methanol and Chiralzyme IM-100 immobilized enzyme, wherein the volume mass ratio of the methanol to the soybean oil deodorized distillate is 0.3: 1(mL/g), adding 70plu/g of soybean oil deodorized distillate into Chiralzyme IM-100 immobilized enzyme, uniformly mixing, reacting at the temperature of 60 ℃, stirring for 3 hours at the rotating speed of 150 revolutions per minute, placing reaction liquid into a separating funnel for layering, taking supernatant, washing the supernatant with water at the temperature of 60 ℃, wherein the mass ratio of the supernatant to washing water is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain a primary esterification product; the method comprises the following steps of adopting a strong-acid cation exchange resin as a catalyst, filling the strong-acid cation exchange resin into a reaction column of a fixed bed, mixing methanol and a primary esterification product to prepare a reaction solution, wherein the weight ratio of the methanol to the primary esterification product is 2: 1, introducing a reaction liquid into a reaction column from bottom to top by using a metering pump, wherein the temperature of the reaction column is 60 ℃, the flow rate is 1.57 mL/min, the contact time is 1 hour, placing the reaction liquid into a separating funnel for layering, taking supernatant liquid, washing the supernatant liquid by using water at the temperature of 60 ℃, and the mass ratio of the supernatant liquid to water for washing is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain a secondary esterification product;

Example 7

The extraction process of high-quality vitamin E comprises the following steps:

(2) weighing soybean oil deodorized distillate, placing the soybean oil deodorized distillate into a reactor, adding methanol and lipase, wherein the volume mass ratio of the methanol to the soybean oil deodorized distillate is 0.3: 1(mL/g), the addition amount of lipase is 70plu/g of soybean oil deodorized distillate, and the lipase is Chiralzyme IM-100 immobilized enzyme and Novozym435 immobilized enzyme in a weight ratio of 1: 1.5, uniformly mixing, stirring and reacting for 3 hours at the temperature of 60 ℃ and the rotating speed of 150 rpm, placing the reaction liquid into a separating funnel for layering, taking supernatant, washing the supernatant with water at the temperature of 60 ℃, wherein the mass ratio of the supernatant to the washing water is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain a primary esterification product; the method comprises the following steps of adopting a strong-acid cation exchange resin as a catalyst, filling the strong-acid cation exchange resin into a reaction column of a fixed bed, mixing methanol and a primary esterification product to prepare a reaction solution, wherein the weight ratio of the methanol to the primary esterification product is 2: 1, introducing a reaction liquid into a reaction column from bottom to top by using a metering pump, wherein the temperature of the reaction column is 60 ℃, the flow rate is 1.57 mL/min, the contact time is 1 hour, placing the reaction liquid into a separating funnel for layering, taking supernatant liquid, washing the supernatant liquid by using water at the temperature of 60 ℃, and the mass ratio of the supernatant liquid to the water is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain a secondary esterification product;

(3) weighing a secondary esterification product into a reaction container, adding methanol and sodium methoxide, wherein the volume mass ratio of the methanol to the secondary esterification product is 0.8: 1(mL/g), wherein the weight of sodium methoxide is 0.05 percent of the weight of a secondary esterification product, the sodium methoxide and the secondary esterification product are uniformly mixed, the mixture is stirred and reacted for 2 hours at the temperature of 70 ℃ at the rotating speed of 150 r/min, after the reaction is finished, a hydrochloric acid aqueous solution with the mass fraction of 5 percent is added, and the weight ratio of the hydrochloric acid aqueous solution to the sodium methoxide is 0.9: 1, placing the mixed solution into a separating funnel for layering after mixing, taking supernatant, washing the supernatant with water at the temperature of 70 ℃, wherein the mass ratio of the supernatant to the water is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain a transesterification product;

Test example 1

The vitamin E content is measured by reference to GB/T5009.82-2003. The vitamin E retention rate is calculated by the formula: retention ═ (m1 × c1)/(m2 × c2) × 100%, m1 is the amount of product, g; c1 is the vitamin E content,%, in the product; m2 is the amount of raw material, g; c2 is the content of vitamin E in the raw material. The specific test results are shown in table 1.

Table 1: vitamin E retention test result table

Test example 2

The physicochemical properties of vitamin E from examples 1-7 were determined and the test indications are ash, refractive index, acid number and heavy metal content.

And (3) determination of ash content: putting the cleaned porcelain crucible into a muffle furnace, firing for 0.5 hour at the temperature of 500-600 ℃, cooling to 200 ℃, taking out the porcelain crucible by using crucible tongs, putting the porcelain crucible into a dryer, cooling to room temperature, and accurately weighing Wo; taking 2-5g of vitamin E, putting the vitamin E into a crucible, weighing W1, moving the crucible into a muffle furnace, burning and ashing at 525 ℃ until the sample is grey, cooling to 200 ℃, taking out the crucible by using crucible tongs, putting the crucible into a dryer, cooling to room temperature, accurately weighing, burning for 1 hour, cooling to 200 ℃, weighing until the difference between the two weighing is not more than 0.5mg, and obtaining constant weight W2. Ash was calculated as follows: coarse ash% ((W2-Wo)/(W1-Wo) × 100%). The muffle furnace is available from Jiandong precision instruments, Inc. of Suzhou, and is of the type SX 2-4-10.

Measurement of refractive index: the test is carried out by referring to a GB/T5527-85 method, and the test instrument adopts an Abbe refractometer with the model number of WYA-2S provided by Shanghai Pingxuan scientific instruments Co.

Determination of acid value: reference is made to GB5530-85, and the specific method is as follows: vitamin E3-5 g (W) was weighed into an Erlenmeyer flask, and diethyl ether: ethanol volume ratio 2: 1, shaking to dissolve the sample, adding three drops of phenolphthalein indicator, titrating with 0.lmol/L alkali liquor until reddish appears, and recording the number of consumed alkali liquor milliliters (V).

And (3) determination of heavy metal content: reference is made to the method GB/T9758.1-1988.

The specific test results are shown in table 2.

Table 2: vitamin E physical and chemical property test result table

Test example 3

The hypolipidemic effect of vitamin E of examples 1-7 was tested. Male SD rats (purchased from soyama, body weight 200 ± 5g, provided by soyama grisewei biotechnology limited, experimental mice were randomly divided into a normal control group and an experimental group, 10 mice per group were fed with a basal diet for 3 days for adaptive feeding, all the tested mice were fed with a high-fat diet except for the normal control group, and the experimental group was fed with 38mg vitamin E daily, administered with 0.1mL of physiological saline, for 45 days, after the feeding, the mice of each group were fasted for 5 hours, blood was drawn from the eye sockets, and serum was immediately centrifuged for measurement.

Determination of serum cholesterol (TC): CHOD-PAP method. The cholesterol kit was purchased from shanghai kexin biotechnology research institute.

Determination of serum Triglycerides (TG): GK-GPO-PAP method. The triglyceride kit was purchased from shanghai kexin biotechnology institute.

Determination of serum Malondialdehyde (MDA): TBA method. The malondialdehyde kit is purchased from Nanjing to build a bioengineering institute.

The specific test results are shown in table 3.

Table 3: blood fat reducing effect test result table

From the above data, it can be seen that the vitamin E retention of example 2 is improved relative to example 1, presumably because the free fatty acids in the deodorized oil distillate of example 1 are substantially converted into fatty acid methyl esters with lower relative boiling points, but the glycerides present in the deodorized oil distillate have a low esterification rate and remain in the form of glycerides, which is not conducive to subsequent removal of sterols and fatty acid methyl esters; example 2 the fatty acid is esterified into fatty acid methyl ester by using concentrated sulfuric acid as a catalyst, and because of the strong oxidizing property and strong acidity of the concentrated sulfuric acid, a carbonization reaction is easy to occur in the reaction process, so that the quality of the obtained vitamin E is relatively poor; example 3 the use of strong acid cation exchange resin as catalyst, mild reaction conditions, less side reactions, simple product after-treatment, easy catalyst and product separation, but lower catalytic efficiency; example 4 with the enzymatic method, both the yield and quality of vitamin E are improved. However, the esterification reaction is a reversible reaction, the esterification and hydrolysis are carried out simultaneously in the reaction process, the esterification products and the generated water in the reaction system are gradually increased along with the reaction, and the esterification reaction is balanced, and the secondary esterification is adopted in the example 5, so that the esterification reaction is fully carried out on the premise of ensuring the quality of the vitamin E.

The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims

1. The extraction process of high-quality vitamin E is characterized by comprising the following steps of:

(3) transesterification of glycerides: weighing an esterification product into a reaction vessel, adding methanol and sodium methoxide, wherein the volume mass ratio of the methanol to the esterification product is (0.7-1) mL: 1g, the weight of sodium methoxide is 0.05-0.06 percent of the weight of esterification products, the mixture is evenly mixed and stirred for reaction for 1-3 hours at the temperature of 65-75 ℃ and the rotating speed of 100 rpm, after the reaction is finished, hydrochloric acid aqueous solution with the mass fraction of 5-10 percent is added, and the weight ratio of the hydrochloric acid aqueous solution to the sodium methoxide is (0.8-0.9): 1, mixing, layering the mixed solution in a separating funnel, taking supernatant, washing the supernatant with water at 65-75 ℃, wherein the mass ratio of the supernatant to the washing water is 1: (5-10), adding anhydrous sodium sulfate which is 0.2-0.3 time of the weight of the supernatant into the washed supernatant, standing for 10-20 minutes, filtering by using 300-plus 500-mesh filter cloth, and drying the filtrate for 1-2 hours under the conditions that the vacuum degree is 0.06-0.07MPa and the temperature is 50-60 ℃ to obtain a transesterification product;

(5) removing fatty acid methyl ester: performing molecular distillation on the filtrate by adopting a wiped film type molecular distiller, wherein the primary distillation temperature is 110-;

in the step (2), the esterification of the free fatty acid in the grease deodorization distillate is carried out twice, and the specific process is as follows: weighing the grease deodorized distillate, placing the grease deodorized distillate into a reactor, adding methanol and lipase, wherein the volume-to-mass ratio (0.25-0.35) mL of the methanol to the grease deodorized distillate is as follows: 1g of grease deodorized distillate with the lipase addition amount of 60-80plu/g, uniformly mixing, stirring and reacting at the temperature of 50-60 ℃ at the rotation speed of 100 plus drugs/min for 3-8 hours, placing the reaction liquid in a separating funnel for layering, taking the upper layer liquid, adding anhydrous sodium sulfate with the weight of 0.2-0.3 time of that of the upper layer liquid into the upper layer liquid, standing for 10-20 minutes, filtering by using 300 plus filter cloth with 500 meshes, and drying the filtrate for 1-2 hours under the conditions of the vacuum degree of 0.06-0.07MPa and the temperature of 50-60 ℃ to obtain a primary esterification product; then, using a strong acid cation exchange resin as a catalyst, filling the strong acid cation exchange resin into a reaction column of a fixed bed, mixing methanol and a primary esterification product to prepare a reaction solution, wherein the mass ratio of the methanol to the primary esterification product is (1.5-2.5): 1, introducing a reaction solution into a reaction column from bottom to top by using a metering pump, wherein the temperature of the reaction column is 50-60 ℃, the flow rate is 1.57-4.18 mL/min, the contact time is 1-2 hours, placing the reaction solution into a separating funnel for layering, taking an upper layer solution, washing the upper layer solution by using water at the temperature of 50-60 ℃, and the mass ratio of the upper layer solution to washing water is 1: (5-10), adding anhydrous sodium sulfate which is 0.2-0.3 time of the weight of the supernatant into the washed supernatant, standing for 10-20 minutes, filtering by using 300-plus 500-mesh filter cloth, and drying the filtrate for 1-2 hours under the conditions that the vacuum degree is 0.06-0.07MPa and the temperature is 50-60 ℃ to obtain a secondary esterification product;

the lipase is Chiralzyme IM-100 immobilized enzyme and Novozym435 immobilized enzyme according to the weight ratio of 1: (1.5-2).

2. The process for extracting high-quality vitamin E according to claim 1, comprising the following steps:

(2) weighing soybean oil deodorized distillate, placing the soybean oil deodorized distillate into a reactor, adding methanol and lipase, wherein the volume-to-mass ratio of the methanol to the soybean oil deodorized distillate is 0.3 mL: 1g, adding 70plu/g of soybean oil deodorized distillate by using lipase, wherein the lipase is Chiralzyme IM-100 immobilized enzyme and Novozym435 immobilized enzyme in a weight ratio of 1: 1.5, uniformly mixing, stirring and reacting for 3 hours at the temperature of 60 ℃ and the rotating speed of 150 rpm, placing the reaction liquid into a separating funnel for layering, taking supernatant, washing the supernatant with water at the temperature of 60 ℃, wherein the mass ratio of the supernatant to the washing water is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain a primary esterification product; the method comprises the following steps of adopting a strong-acid cation exchange resin as a catalyst, filling the strong-acid cation exchange resin into a reaction column of a fixed bed, mixing methanol and a primary esterification product to prepare a reaction solution, wherein the weight ratio of the methanol to the primary esterification product is 2: 1, introducing a reaction liquid into a reaction column from bottom to top by using a metering pump, wherein the temperature of the reaction column is 60 ℃, the flow rate is 1.57 mL/min, the contact time is 1 hour, placing the reaction liquid into a separating funnel for layering, taking supernatant liquid, washing the supernatant liquid by using water at the temperature of 60 ℃, and the mass ratio of the supernatant liquid to the water is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain a secondary esterification product;

(3) weighing a secondary esterification product into a reaction container, adding methanol and sodium methoxide, wherein the volume mass ratio of the methanol to the secondary esterification product is 0.8 mL: 1g of sodium methoxide, wherein the weight of the sodium methoxide is 0.05 percent of the weight of a secondary esterification product, the sodium methoxide and the secondary esterification product are uniformly mixed, the mixture is stirred and reacted for 2 hours at the temperature of 70 ℃ at the rotating speed of 150 rpm, after the reaction is finished, a hydrochloric acid aqueous solution with the mass fraction of 5 percent is added, and the weight ratio of the hydrochloric acid aqueous solution to the sodium methoxide is 0.9: 1, placing the mixed solution into a separating funnel for layering after mixing, taking supernatant, washing the supernatant with water at the temperature of 70 ℃, wherein the mass ratio of the supernatant to the water is 1: 10, adding anhydrous sodium sulfate which is 0.3 time of the weight of the supernatant into the washed supernatant, standing for 20 minutes, filtering by adopting 300-mesh filter cloth, and drying the filtrate for 1 hour under the conditions of vacuum degree of 0.06MPa and temperature of 50 ℃ to obtain a transesterification product;

3. The process of claim 1, wherein the deodorized oil distillate is soybean oil deodorized distillate, rapeseed oil deodorized distillate, peanut oil deodorized distillate or palm oil deodorized distillate.