阅读说明：本技术 一种使用分子蒸馏技术从茶油脱臭馏出物中提取维生素e的方法 (Method for extracting vitamin E from tea oil deodorized distillate by using molecular distillation technology ) 是由 付建平 韩晓丹 熊伟 吴磊 王慧宾 于 2019-09-05 设计创作，主要内容包括：本发明公开了一种使用分子蒸馏技术从茶油脱臭馏出物中提取维生素E的方法,其步骤包括,(1)酯化预处理；(2)一级分子蒸馏；(3)二级分子蒸馏；(4)三级分子蒸馏。本发明通过正交试验法对分子蒸馏实验条件进行优化。实验表明,蒸发温度为200℃,进料速率为4mL/min,刮膜转速为150rpm时,产物维生素E的纯度达到最高,为0.93％。应用高效液相色谱法对原料成分进行分析,建立了从原料到产品的生育酚含量分析方法。高效液相色谱法分析生育酚含量,原料无需预处理,操作简易,准确率高。(The invention discloses a method for extracting vitamin E from deodorized distillate of tea oil by using a molecular distillation technology, which comprises the following steps of (1) esterification pretreatment; (2) primary molecular distillation; (3) secondary molecular distillation; (4) and (3) three-stage molecular distillation. The invention optimizes the molecular distillation experimental conditions by an orthogonal experimental method. Experiments show that when the evaporation temperature is 200 ℃, the feeding rate is 4mL/min, and the rotating speed of a film scraper is 150rpm, the purity of the product vitamin E reaches the highest value, namely 0.93%. The high performance liquid chromatography is used for analyzing the components of the raw materials, and a method for analyzing the content of tocopherol from the raw materials to the product is established. The high performance liquid chromatography is used for analyzing the content of the tocopherol, the raw materials do not need to be pretreated, the operation is simple and easy, and the accuracy is high.)

1. A method for extracting vitamin E from deodorized distillate of tea oil by molecular distillation comprises,

(1) esterification pretreatment: according to the weight ratio of alcohol oil of 1: 1.4-1.8 adding a tea oil deodorized distillate raw material into ethanol, then adding a catalyst accounting for 10-30% of the weight of the mixed solution and a molecular sieve accounting for 15-25% of the weight of the mixed solution, stirring and reacting at 50-70 ℃ for 4.5-6.5 hours, and washing a reaction product to obtain a mixture taking vitamin E and fatty acid ethyl ester as main components;

(2) primary molecular distillation: performing primary molecular distillation on 500g of molecular distillation raw material obtained by pretreatment in the step (1), wherein the preheating temperature is 40-70 ℃; under the conditions that the system pressure is 0.1Pa, the heating wall surface temperature is 80-100 ℃, and the scraper rotating speed is 80-110 rpm, the heavy phase of a primary molecular distillation product is obtained by entering the molecular distillation device at a feeding rate of 5-7 mL/min, and light phase components with low boiling points such as aldehyde, ketone, carbohydrate and the like are mainly removed;

(3) secondary molecular distillation: carrying out secondary molecular distillation on a heavy phase obtained from the primary molecular distillation product, wherein the preheating temperature is 75-95 ℃; under the conditions that the system pressure is 0.1Pa, the heating wall surface temperature is 120-150 ℃, and the scraper plate rotating speed is 90-110 rpm, the mixture enters a molecular distillation device at a feeding rate of 3-5 mL/min to obtain a secondary molecular distillation product; collecting heavy phase components in the process, and removing light phase components with low boiling points such as rich fatty acid ethyl ester;

(4) three-stage molecular distillation: subjecting the heavy phase obtained from the second molecular distillation product to a third molecular distillation to separate vitamin E and triglyceride; under the condition that the system pressure is 0.1Pa, the heating wall surface temperature is 160-240 ℃, and the film scraping rotating speed is 100-200 rpm, the mixture enters a molecular distillation device at a feeding rate of 2-4 mL/min, vitamin E in a light phase is collected, and the content of the vitamin E in a product is used as a detection index.

2. The method for extracting vitamin E from the tea oil deodorizer distillate using molecular distillation as claimed in claim 1, wherein in step (1), the catalyst is preferably cation exchange resin of south opening 001 x 7 type; the molecular sieve is used as a water absorbent, and the molecular sieve is a spherical 5A type molecular sieve.

3. The method for extracting vitamin E from the deodorized distillate of tea oil using molecular distillation as claimed in claim 1, wherein the weight ratio of ethanol to deodorized distillate of tea oil in step (1) is 1: 1.5, the mass fraction of the catalyst is 20%, the reaction temperature is 50 ℃, the reaction time is 6 hours, and the esterification rate of the deodorized distillate of the tea oil reaches 96.2%.

4. The method for extracting vitamin E from a tea oil deodorizer distillate using a molecular distillation technique as claimed in claim 1, wherein after the step (1), the mixture obtained in the step (1) is subjected to ultrasonic treatment and then to low-temperature freezing recrystallization, and the molecular distillation raw material is further purified by filtering to remove crystals.

5. The method for extracting vitamin E from tea oil deodorizer distillate by using molecular distillation technology as claimed in claim 1, wherein in step (2), the process parameters are preheating temperature 55-65 ℃, system pressure 0.1Pa, heating wall temperature 80-95 ℃, scraper rotation speed 95-110 rpm, and feeding rate 5.5-7 mL/min.

6. The method for extracting vitamin E from tea oil deodorizer distillate by molecular distillation as claimed in claim 1, wherein in step (2), the process parameters are preheating temperature 85 deg.C, system pressure 0.1Pa, heating wall temperature 90 deg.C, scraper rotation speed 100rpm, and feed rate 6 mL/min.

7. The method for extracting vitamin E from tea oil deodorizer distillate by molecular distillation as claimed in claim 1, wherein in step (3), the process parameters are preheating temperature of 90 deg.C, system pressure of 0.1Pa, heating wall temperature of 135 deg.C, scraper rotation speed of 100rpm, and feed rate of 4 mL/min.

8. The method for extracting vitamin E from the deodorized distillate of tea oil by molecular distillation as claimed in claim 1, wherein in step (4), the process parameters are that the temperature of the heating wall surface is 200 ℃, the rotating speed of the wiped film is 150rpm, the feeding rate is 4mL/min, the heavy phase is triglyceride, and the light phase is vitamin E.

9. The method for extracting vitamin E from deodorized distillate of tea oil by molecular distillation as claimed in claim 1, wherein in steps (2), (3) and (4), before starting molecular distillation, the tightness of each vent valve is checked, and the cold trap is filled with liquid nitrogen to better ensure vacuum degree and protect oil diffusion pump.

Technical Field

The invention belongs to the technical field of vitamin E extraction from tea oil deodorized distillate, and particularly relates to a method for extracting vitamin E from tea oil deodorized distillate by a molecular distillation technology.

Background

The oil tea seed oil can reach consumers only by refining procedures of degumming, deacidification, decoloration, deodorization and the likeAnd (5) eating requirements. The oil and fat is deodorized to produce deodorized distillate with free fatty acid, glyceride, natural vitamin E, sterol ester and oxidation product as main components, and the most developed natural vitamin E is. Natural vitamin E is a mixture of four tocopherols and four tocotrienols, and is classified into alpha-, beta-, gamma-, delta-tocopherols and alpha-, beta-, gamma-, delta-tocotrienols according to the difference of the number of positions methylated on the benzene ring. Vitamin E has various physiological function activities, and can be widely applied to industries such as cosmetics, medicines, foods and the like. The camellia seed oil contains abundant vitamin E, however, after crude oil is refined, the loss of nutrient substances such as the vitamin E is found to be large, the quality of the camellia oil is directly reduced, and most of the loss of the camellia oil is remained in soapstock and deodorized distillate. The byproducts in the tea oil processing process are comprehensively utilized, active substances in the tea oil are extracted, waste materials are changed into valuable materials, and the tea oil processing method has important research and economic values. At present, the domestic method for preparing natural high-content vitamin E by using grease as a raw material mainly comprises a supercritical extraction method (SFE), a molecular distillation Method (MD) and the like. Supercritical CO₂The extraction (SCDE) has the advantages of strong extraction capability, no toxicity, safety, wide sources, easy removal from products and the like, and is a green extraction technology which is developed rapidly in recent years. But the deodorized distillate has high content of nonvolatile components and coloring matter substances, these nonvolatile components are mainly unsaturated fatty acids and are liable to undergo autooxidation, and further the coloring matter also affects the storage of the essential oil, so that the quality of the supercritical extract deteriorates rapidly and the storage period is short. Molecular distillation techniques rely on the difference in the mean free path of movement of the molecules of a mixture to separate them at temperatures well below their boiling points. Therefore, the molecular distillation technology is particularly suitable for separating high boiling point, heat sensitivity and easy oxide systems. The method is intended to adopt a multistage molecular distillation technology to extract natural vitamin E in the deodorized distillate of the tea oil so as to provide a theoretical basis for industrial production, carry out waste utilization and make a contribution to environmental protection.

Disclosure of Invention

The invention aims to provide a method for extracting high-purity vitamin E from tea oil deodorizer distillate. The method takes the deodorized distillate of the tea oil as a raw material, adopts cation exchange resin to catalyze esterification reaction, and then carries out tertiary molecular distillation on the esterification product to gradually remove fatty acid and a small amount of other impurities.

The invention solves the technical problems through the following technical scheme,

a method for extracting vitamin E from deodorized distillate of tea oil by molecular distillation comprises,

(1) esterification pretreatment: according to the weight ratio of alcohol oil of 1: 1.4-1.8 adding a tea oil deodorized distillate raw material into ethanol, then adding a catalyst accounting for 10-30% of the weight of the mixed solution and a molecular sieve accounting for 15-25% of the weight of the mixed solution, stirring and reacting at 50-70 ℃ for 4.5-6.5 hours, and washing a reaction product to obtain a mixture taking vitamin E and fatty acid ethyl ester as main components;

(2) primary molecular distillation: performing primary molecular distillation on 500g of molecular distillation raw material obtained by pretreatment in the step (1), wherein the preheating temperature is 40-70 ℃; under the conditions that the system pressure is 0.1Pa, the heating wall surface temperature is 80-100 ℃, and the scraper rotating speed is 80-110 rpm, the heavy phase of a primary molecular distillation product is obtained by entering the molecular distillation device at a feeding rate of 5-7 mL/min, and light phase components with low boiling points such as aldehyde, ketone, carbohydrate and the like are mainly removed;

(3) secondary molecular distillation: carrying out secondary molecular distillation on a heavy phase obtained from the primary molecular distillation product, wherein the preheating temperature is 75-95 ℃; under the conditions that the system pressure is 0.1Pa, the heating wall surface temperature is 120-150 ℃, and the scraper plate rotating speed is 90-110 rpm, the mixture enters a molecular distillation device at a feeding rate of 3-5 mL/min to obtain a secondary molecular distillation product; collecting heavy phase components in the process, and removing light phase components with low boiling points such as rich fatty acid ethyl ester;

(4) three-stage molecular distillation: subjecting the heavy phase obtained from the second molecular distillation product to a third molecular distillation to separate vitamin E and triglyceride; under the condition that the system pressure is 0.1Pa, the heating wall surface temperature is 160-240 ℃, and the film scraping rotating speed is 100-200 rpm, the mixture enters a molecular distillation device at a feeding rate of 2-4 mL/min, vitamin E in a light phase is collected, and the content of the vitamin E in a product is used as a detection index.

As a preferred technical solution, in the step (1), the catalyst is preferably a south-opening 001 x 7 type cation exchange resin; the molecular sieve is used as a water absorbent, and the molecular sieve is a spherical 5A type molecular sieve.

As a preferable technical scheme, in the step (1), the weight ratio of ethanol to the tea oil deodorized distillate is preferably 1: 1.5, the mass fraction of the catalyst is 20%, the reaction temperature is 50 ℃, the reaction time is 6 hours, and the esterification rate of the deodorized distillate of the tea oil reaches 96.2%.

As a preferable technical scheme, after the step (1), the mixture obtained in the step (1) is subjected to ultrasonic treatment and then low-temperature freezing recrystallization, and the molecular distillation raw material is further purified by filtering to remove crystals.

As an optimal technical scheme, in the step (2), the optimal technological parameters are that the preheating temperature is 55-65 ℃, the system pressure is 0.1Pa, the heating wall surface temperature is 80-95 ℃, the scraper rotating speed is 95-110 rpm, and the feeding rate is 5.5-7 mL/min.

As a preferred technical scheme, in the step (2), the process parameters are preferably that the preheating temperature is 85 ℃, the system pressure is 0.1Pa, the heating wall surface temperature is 90 ℃, the scraper rotating speed is 100rpm, and the feeding rate is 6 mL/min. .

As a preferred technical scheme, in the step (3), the process parameters are preferably that the preheating temperature is 90 ℃, the system pressure is 0.1Pa, the heating wall surface temperature is 135 ℃, the scraper rotating speed is 100rpm, and the feeding rate is 4 mL/min.

As a preferable technical scheme, before the steps (2), (3) and (4) and before the molecular distillation is started, the tightness of each exhaust valve is checked, and the cold trap is ensured to be filled with liquid nitrogen so as to better ensure the vacuum degree and protect an oil diffusion pump.

As a preferred technical scheme, in the step (4), the technological parameters are preferably that the temperature of the heating wall surface is 200 ℃, the film scraping rotating speed is 150rpm, the feeding speed is 4mL/min, the heavy phase is triglyceride, and the light phase is vitamin E.

The molecular distillation experimental conditions were optimized by orthogonal experimental method. Experiments show that when the evaporation temperature is 200 ℃, the feeding rate is 4mL/min, and the rotating speed of a film scraper is 150rpm, the purity of the product vitamin E reaches the highest value, namely 0.93%. The high performance liquid chromatography is used for analyzing the components of the raw materials, and a method for analyzing the content of tocopherol from the raw materials to the product is established. The high performance liquid chromatography is used for analyzing the content of the tocopherol, the raw materials do not need to be pretreated, the operation is simple and easy, and the accuracy is high.

Drawings

FIG. 1 is a vitamin E standard HPLC chromatogram of an embodiment of the present invention.

Detailed Description

The invention is explained in further detail below with reference to the figures and examples.

The embodiment of the invention selects the following instruments:

molecular distillation apparatus of KDL5 type, UIC, Germany;

HY-8(A) type oscillator;

model TDL-40B desk high capacity centrifuge;

german sykam liquid chromatograph;

shanghai Yangrong Biochemical Instrument plant RE52CS-1 rotary evaporator;

DHG-9076A electric heating constant temperature air drying oven of Shanghai essence macro experimental facility Limited;

KQ-2200 ultrasonic cleaner of ultrasonic apparatus Limited of Kunshan city;

sadoris scientific instruments, Beijing, Inc. ALB-224 analytical balance, etc.

The embodiment of the invention selects the following reagents:

dry hydrogen strong acid cation exchange resin;

the ether, the ethanol, the potassium hydroxide and the anhydrous sodium sulfate are analytically pure;

chromatographic grade methanol;

a molecular sieve;

alpha-tocopherol, beta-tocopherol standards;

the distillate for deodorizing tea oil is provided by Wanshan tea-oil tea Co., Ltd.