CN113789354A - Preparation technology of edible oil diglyceride - Google Patents
Preparation technology of edible oil diglyceride Download PDFInfo
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- CN113789354A CN113789354A CN202111088006.5A CN202111088006A CN113789354A CN 113789354 A CN113789354 A CN 113789354A CN 202111088006 A CN202111088006 A CN 202111088006A CN 113789354 A CN113789354 A CN 113789354A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/6445—Glycerides
- C12P7/6454—Glycerides by esterification
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/02—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils
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- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/02—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils
- C11C1/025—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by saponification and release of fatty acids
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/02—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with glycerol
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Abstract
一种食用油二甘酯的制取工艺，包括下述步骤：（1）以食用油为原料进行皂化反应，得到皂液；（2）向皂液中加入过量的硫酸或磷酸，进行酸化反应，得到脂肪酸粗液；（3）将脂肪酸粗液加水进行水洗，水洗结束后静置，再将上层的脂肪酸与下层的水分离；（4）对脂肪酸进行真空干燥；（5）将脂肪酸与甘油按1.5:1‑2.5:1的摩尔比混合均匀，得到第一混合物料；然后将第一混合物料加入到固定化酶柱中，在温度50‑55℃的条件下反应2‑4小时；（6）采用分子蒸馏装置，对步骤（5）的反应产物进行分子蒸馏，分子蒸馏获得的重组分即为所需的食用油二甘酯。本发明采用直接酯化法获得甘油二酯，其原料易得，生产成本较低，且产物得率高，产物纯度高。A process for preparing edible oil diglyceride, comprising the following steps: (1) using edible oil as a raw material to carry out saponification reaction to obtain soap liquid; (2) adding excess sulfuric acid or phosphoric acid to the soap liquid to carry out acidification reaction , obtain the fatty acid crude liquid; (3) add water to the fatty acid crude liquid and wash with water, leave standstill after washing, and then separate the fatty acid in the upper layer from the water in the lower layer; (4) vacuum drying the fatty acid; (5) by the fatty acid and glycerol Mix uniformly at a molar ratio of 1.5:1-2.5:1 to obtain the first mixed material; then add the first mixed material to the immobilized enzyme column, and react for 2-4 hours at a temperature of 50-55°C; ( 6) Use a molecular distillation device to perform molecular distillation on the reaction product of step (5), and the heavy component obtained by molecular distillation is the desired edible oil diglyceride. The present invention adopts the direct esterification method to obtain the diglyceride, the raw material is easy to obtain, the production cost is low, the product yield is high, and the product purity is high.
Description
Technical Field
The invention relates to the technical field of oil modification, in particular to a preparation process of edible oil diglyceride.
Background
Diglycerides (also known as diglycerides) are the products of the esterification of glycerol with two fatty acids. Diglyceride is a natural component of animal and vegetable oil and fat, but the content of diglyceride is generally low, and the content of diglyceride in different oil and fat is different, and is generally between 4 and 8 percent, so that high content of diglyceride is generally obtained by a chemical method or a biological enzyme method. The diglyceride has special physiological functions due to different metabolic pathways with triglyceride, and can reduce fat accumulation, reduce obesity, and reduce postprandial blood lipid content, thereby preventing and treating hyperlipemia, hypertension, cardiovascular disease and cerebrovascular disease, etc. The diglyceride can provide fatty acid and energy needed by human body, and also keep the special flavor of the grease, and meanwhile, the absorption of fat-soluble nutrient substances is not influenced. The edible oil diglyceride is an oil mixture obtained by using edible oils such as soybean oil, peanut oil, corn oil, rapeseed oil, sunflower seed oil, palm oil, lard and the like as raw materials and increasing the content of diglyceride by a biological enzyme method or a chemical method.
In 1998, cooking oil containing diglyceride as a main component was approved as a "special health food" by the japan ministry of health and welfare, and was approved as a GRAS food by the us food and drug administration (FAD) in 2000. In 2004, canada officials identified diglycerides as new resource foods by legislation; at the same time, the australian food standards institute, through a safety assessment of diglycerides, clearly dictates that the diglyceride component can be added. In 2005, the european union food safety agency (EFSA) passed resolution of diglycerides, and it was recognized as a new resource food, which was allowed to be put on the market. In 2009, 12 and 22 days, diglyceride is listed as a new resource food in China.
Due to its unique physical and chemical properties and physiological functions, diglycerides are widely used in the food, pharmaceutical, cosmetic and other industries. Diacylglycerol-rich fats and oils have been marketed in japan and the united states market and sold as "special healthy fats and oils". Diglycerides are used in the food industry as a replacement for triglycerides, including frying oil, cooking oil, salad dressing, mayonnaise, shortening, butter, chocolate, ice cream, candy, bakery products, beverages, and the like.
Fatty acids and mono-and diglycerides can be separated from the product mixture by molecular distillation due to their large difference in physical properties, but triglycerides and diglycerides are difficult to separate due to their close molecular weight, molecular motion mean free path, etc. Therefore, in order to obtain high-purity diglycerides, the formation of triglycerides should be avoided as much as possible in the reaction for preparing diglycerides.
At present, most of the methods for preparing diglyceride are carried out in a lipase catalysis mode. The lipase has various catalysis modes, and can catalyze a plurality of reactions such as hydrolysis, esterification, ester exchange and the like. In terms of the nature of the reaction, the production methods of diglycerides mainly include hydrolysis, transesterification, glycerolysis, direct esterification, and the like.
1. Hydrolysis method
The hydrolysis method is that the triglyceride produces diglyceride and fatty acid through enzyme catalysis, and the triglyceride in the natural animal and vegetable oil is subjected to limited hydrolysis to obtain the oil product containing the diglyceride. However, the process route for producing diglyceride products by the hydrolysis method has obvious disadvantages in large-scale application: firstly, hydrolysis reaction produces a large amount of by-products, free fatty acids and a certain amount of glycerol; secondly, the yield of diglycerides in the diglyceride product is generally low (around 30%), while a large amount of triglycerides remains in the hydrolysate, and the content of diglycerides in the final product is low (not more than 70% at most) because separation of triglycerides from diglycerides is difficult. The hydrolysis method can produce a large amount of free fatty acid in the process of producing diglyceride, reduces the yield of diglyceride, also brings heavy pressure to the subsequent separation and refining processes, and is not an optimal process for industrially producing diglyceride.
2. Transesterification process
The transesterification method mainly utilizes the acyl transfer between triglyceride, monoglyceride or fatty acid methyl ester with different fatty acid compositions to produce diglyceride, and is mixed with common oil to carry out transesterification to produce diglyceride, the reaction time is short, the product purity is high, the transesterification method is widely applied in the existing medicine, food and chemical industries, and the defect is that the transesterification efficiency is low.
3. Glycerol splitting method
The glycerolysis method is a method for catalytically synthesizing diglyceride from triglyceride and glycerol under the action of enzyme. The glycerolysis process is currently the method used mainly in industry and is the most economical process for the production of diglycerides. Although the glycerolysis method has low cost, the product purity is not high, the reaction speed is slow, the yield is low, and therefore, the application effect in industrial production is not satisfactory. The addition of the organic solvent is one of effective ways for solving the problems of immiscible substrates, overlarge viscosity and the like in the glycerolysis system, but the requirements of food industry and production safety limit the application of the glycerolysis reaction of the organic solvent system in actual production.
4. Direct esterification process
The direct esterification method is to take acyl donor (fatty acid) and glycerin as raw materials, control the proportion of the acyl donor and the glycerin, and catalyze and synthesize diglyceride by using lipase under the condition of slight water. The direct esterification method has the following outstanding advantages: the reaction can be completed in one step, the product purity is high, the separation is easy, the reaction time is short, and the utilization rate of the enzyme reactor is high, so that the method has better industrialization potential. However, the method has the problems that reaction raw materials need to be prepared respectively and the cost is high.
The partial glyceride Lipase can catalyze the esterification of fatty acid and glycerol, the obtained product only contains fatty acid, monoglyceride and diglyceride, and triglyceride is not existed, the partial glyceride Lipase is an ideal catalyst for preparing high-purity diglyceride and monoglyceride products, but the partial glyceride Lipase is difficult to obtain, most partial glyceride lipases are in the laboratory stage at present and cannot be used commercially, and only Lipase 'Amano' G50 of Japanese wild enzyme product group has a small supply, so the price is high, and the production cost is greatly increased.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a process for preparing edible oil diglyceride, which adopts a direct esterification method to obtain diglyceride, and has the advantages of easily obtained raw materials, lower production cost, high product yield and high product purity. The technical scheme is as follows:
a preparation process of edible oil diglyceride is characterized by comprising the following steps:
(1) saponification reaction
Performing saponification reaction on edible oil serving as a raw material to obtain a soap solution;
(2) acidification reaction
Adding excessive sulfuric acid or phosphoric acid into the soap solution obtained in the step (1) to carry out an acidification reaction to obtain a fatty acid crude solution;
(3) washing with water
Pouring the crude fatty acid solution obtained in the step (2) into a water washing tank, adding water for washing, standing after the washing is finished, and separating the upper fatty acid layer from the lower fatty acid layer;
(4) vacuum drying
Vacuum drying the fatty acid obtained in the step (3);
(5) esterification reaction
Uniformly mixing the fatty acid obtained in the step (4) and glycerol according to a molar ratio of 1.5:1-2.5:1 to obtain a first mixed material; then adding the first mixed material into an immobilized enzyme column, and reacting for 2-4 hours at the temperature of 50-55 ℃;
(6) molecular distillation
And (3) performing molecular distillation on the reaction product obtained in the step (5) by adopting a molecular distillation device under the conditions that the distillation temperature is 140-160 ℃ and the vacuum degree is less than 1Pa, wherein the heavy component obtained by the molecular distillation is the needed edible oil diethylene glycol.
Preferably, in step (1), the edible oil is one or more of soybean oil, peanut oil, corn oil, rapeseed oil, sunflower seed oil, palm oil and lard.
Preferably, in the step (1), water and sodium hydroxide are added into the edible oil, the weight ratio of the water to the edible oil is 1:1-1:3, and the addition amount of the sodium hydroxide is 12-18% of the weight of the edible oil; the saponification reaction is carried out under the condition of stirring, the reaction temperature of the saponification reaction is 75-85 ℃, and the reaction time is 2-4 hours. More preferably, in step (1), the stirring speed is 200-300 revolutions per minute (rpm).
And (2) after the sodium hydroxide and the edible oil are subjected to saponification reaction in the step (1), generating sodium aliphatate and glycerol.
Preferably, in the step (2), the acidification reaction is carried out under the condition of stirring, the reaction temperature of the acidification reaction is 75-85 ℃, and the reaction time is 0.5-1 hour. More preferably, in step (2), the stirring speed is 200-300 rpm.
And (3) carrying out an acidification reaction on the sodium fatty acid and sulfuric acid or phosphoric acid in the step (2) to generate fatty acid and sodium sulfate or sodium phosphate. Excess sulfuric or phosphoric acid means that it contains hydrogen ions H+Is greater than the moles of sodium ions.
In the preferable step (3), the washing method comprises the following steps: adding 0.5-1 times of water (preferably 75-85 deg.C water) into the fatty acid crude liquid obtained in step (2), heating while stirring, boiling, and stirring for 10-30 min.
Preferably, in the step (3), the mixture is allowed to stand for 0.5 to 1 hour after the washing with water is completed.
Preferably, in step (3), the water washing is performed 3 times, namely: and (3) carrying out secondary washing and separation on the fatty acid obtained after the primary washing and separation, and carrying out tertiary washing and separation on the fatty acid obtained after the secondary washing and separation, wherein the obtained fatty acid enters the next working procedure.
The purpose of the water washing in the step (3) is to remove sodium sulfate or sodium phosphate and redundant acid in the crude fatty acid solution.
Preferably, in the step (4), the fatty acid obtained in the step (3) is placed in a closed tank, the degree of vacuum in the closed tank is reduced to less than 200Pa by evacuation, and water contained in the fatty acid is removed by heating. More preferably, the heating temperature used for vacuum drying is 60 to 100 ℃.
In the step (5), immobilized lipase is filled in the immobilized enzyme column. Preferably, the flow rate of the first mixed material in the immobilized enzyme column is 200-1000L/h.
In a preferable embodiment, in the step (5), the immobilized enzyme column has a plurality of columns, and the plurality of columns are arranged side by side. A plurality of immobilized enzyme columns arranged side by side are adopted for enzymolysis, so that the reaction efficiency can be improved. Reference is made to the "an enzyme reactor apparatus" disclosed in a prior patent application with the applicant company patent No. cn202020484401.x for a more specific structure of the apparatus for carrying out the esterification reaction.
In another preferred embodiment, in the step (5), a plurality of immobilized enzyme columns are provided, and the plurality of immobilized enzyme columns are sequentially connected end to end.
In one embodiment, each immobilized enzyme column has a volume of 50L, and each column is filled with 10-20kg of immobilized lipase.
Preferably, in the step (5), edible oil is further added to the fatty acid and the glycerol, the weight of the added edible oil is 5-10% of that of the fatty acid, and the fatty acid, the glycerol and the edible oil are uniformly mixed to obtain a first mixed material. Through multiple experimental researches, the direct esterification method is adopted to react fatty acid with glycerol to obtain diglyceride, more diglyceride is further converted into triglyceride in the reaction process, more triglyceride is generated (the triglyceride accounts for 10-18% of the total product), and the utilization rate of free fatty acid is reduced; in further experimental research, it is found that the addition of 5-10% of edible oil (the main component of which is triglyceride) before the direct esterification of fatty acids and glycerol can inhibit the conversion of diglyceride to triglyceride, which is beneficial to improving the utilization rate of free fatty acids. The utilization of free fatty acids means the percentage of fatty acids converted to diglycerides based on the total amount of free fatty acids added.
Preferably, the edible oil added in step (5) is one or more of soybean oil, peanut oil, corn oil, rapeseed oil, sunflower seed oil, palm oil and lard. More preferably, the edible oil added in step (5) is the same as the edible oil used in step (1).
Preferably, in the step (6), the molecular distillation is carried out at a molecular distillation feed rate of 100-300L/h.
The light components obtained by molecular distillation in the step (6) mainly comprise fatty acid, glycerol, monoglyceride and the like, and the components can be used as raw materials for producing diglyceride again, so that the waste of the raw materials is caused by directly discarding the components.
In a preferable scheme, the preparation process of the edible oil diglyceride further comprises the step (7) of circulating reaction: mixing the light component obtained by molecular distillation in the step (6) with a newly prepared first mixed material, wherein the weight of the newly prepared first mixed material is 3-5 times of that of the light component, and performing molecular distillation again after esterification reaction on the obtained mixture; the reaction is circulated for 8-25 times. The newly blended first mixed material is a first mixed material obtained by uniformly mixing the fatty acid obtained in the step (3) and the glycerol according to the molar ratio of 1.5:1-2.5:1, or a first mixed material obtained by uniformly mixing the fatty acid, the glycerol and the added edible oil. In the step (7), the esterification reaction and the molecular distillation in the cyclic reaction can be performed respectively according to the step (5) and the step (6). Through the cyclic reaction in the step (7), raw materials can be fully utilized, and the yield of the final product is improved (through the cyclic reaction, the yield can reach more than 90 percent).
The invention adopts the direct esterification method to obtain the diglyceride, the reaction can be completed in one step, and then the high-purity diglyceride is obtained by the molecular distillation method, the product yield is high, and the reaction time is short; the content of grease diglyceride in the obtained product reaches more than 80 percent, and the product purity is high. In addition, the invention takes common edible oil such as soybean oil, peanut oil, corn oil, rapeseed oil, sunflower seed oil, palm oil, lard oil and the like as raw materials, and obtains fatty acid through saponification reaction and acidification reaction, thereby effectively reducing the raw material cost for synthesizing diglyceride by a direct esterification method, and the fatty acid composition of the edible oil diglyceride product is not obviously changed relative to the raw materials of the edible oil, still keeping better nutritional value and ensuring the quality.
Meanwhile, the immobilized lipase is easy to separate from a reaction product by adopting an immobilized enzyme column in the esterification reaction, the stability of the enzyme can be improved, the loss of the immobilized lipase is effectively reduced, the immobilized lipase can be recycled, the loss of the immobilized lipase and the reduction and minimization of the enzyme activity are realized, the recycling maximization is realized, the reaction efficiency can be greatly improved, the use frequency of the immobilized lipase can reach more than 30 times, and the enzyme cost is greatly reduced.
Detailed Description
Example 1
In this embodiment, the preparation process of edible oil diglyceride includes the following steps:
(1) saponification reaction
Performing saponification reaction on soybean oil serving as a raw material to obtain a soap solution;
in the step (1), water and sodium hydroxide are added into the soybean oil, the weight ratio of the water to the soybean oil is 1:2, and the addition amount of the sodium hydroxide is 15 percent of the weight of the soybean oil; carrying out saponification reaction under the condition of stirring (the stirring speed is 200 r/min), wherein the reaction temperature of the saponification reaction is 78 ℃, and the reaction time is 4 hours;
(2) acidification reaction
Adding excessive sulfuric acid into the soap solution obtained in the step (1) to carry out an acidification reaction to obtain a fatty acid crude solution;
in the step (2), an acidification reaction is carried out under the condition of stirring (the stirring speed is 200 revolutions per minute), the reaction temperature of the acidification reaction is 75 ℃, and the reaction time is 0.5 hour;
(3) washing with water
Pouring the crude fatty acid solution obtained in the step (2) into a water washing tank, adding water for washing, standing after the washing is finished, and separating the upper fatty acid layer from the lower fatty acid layer;
in the step (3), the washing method comprises the following steps: adding 0.5 times of water (80 deg.C) into the fatty acid crude liquid, heating under stirring, boiling, and stirring for 20 min; standing for 1 hour after the water washing is finished;
in the step (3), the washing is performed for 3 times, that is: washing and separating the fatty acid obtained after the first washing and separation for the second time, washing and separating the fatty acid obtained after the second washing and separation for the third time, and feeding the obtained fatty acid into the next working procedure;
(4) vacuum drying
Vacuum drying the fatty acid obtained in the step (3);
in the step (4), the fatty acid obtained in the step (3) is put into a closed tank, the vacuum degree in the closed tank is 100Pa through vacuumizing, and water contained in the fatty acid is removed through heating (the heating temperature adopted in vacuum drying is 80 ℃);
(5) esterification reaction
Mixing the fatty acid obtained in the step (4) with glycerol according to a molar ratio of 2:1, adding soybean oil into the fatty acid and the glycerol, wherein the weight of the soybean oil is 8% of that of the fatty acid, and uniformly mixing the fatty acid, the glycerol and the soybean oil to obtain a first mixed material; then adding the first mixed material into an immobilized enzyme column, and reacting for 3 hours at the temperature of 52 ℃;
in the step (5), 4 immobilized enzyme columns are provided, the volume of each immobilized enzyme column is 50L, 15kg of immobilized lipase is filled in each column, and the 4 columns are arranged side by side; the flow rate of the first mixed material in the immobilized enzyme column is 800L/h;
(6) molecular distillation
And (3) performing molecular distillation on the reaction product obtained in the step (5) by adopting a molecular distillation device under the conditions of the distillation temperature of 150 ℃ and the vacuum degree of 0.5Pa (when the molecular distillation is performed, the feeding amount of the molecular distillation is 200L/h), wherein the heavy component obtained by the molecular distillation is the needed edible oil diglyceride.
The preparation process of the edible oil diglyceride can also comprise the step (7) of circulating reaction: mixing the light component obtained by molecular distillation in the step (6) with a newly prepared first mixed material, wherein the weight of the newly prepared first mixed material is 5 times that of the light component, and performing molecular distillation again after esterification reaction on the obtained mixture; the reaction is circulated for 12 times. The newly blended first mixed material is the first mixed material obtained by uniformly mixing the fatty acid, the glycerol and the soybean oil according to the proportion in the step (3). The esterification reaction and the molecular distillation in the cyclic reaction in the step (7) were carried out with reference to the step (5) and the step (6), respectively, except that the reaction time of the esterification reaction in the cyclic reaction was 2.5 hours. After 12 times of circulating reaction, the yield reaches 91.5 percent, and the content of diglyceride in the final product is 85.15 percent.
Example 2
In this embodiment, the preparation process of edible oil diglyceride includes the following steps:
(1) saponification reaction
Performing saponification reaction on corn oil serving as a raw material to obtain a soap solution;
in the step (1), water and sodium hydroxide are added into the corn oil, the weight ratio of the water to the corn oil is 1:2.5, and the adding amount of the sodium hydroxide is 16 percent of the weight of the corn oil; carrying out saponification reaction under the condition of stirring (the stirring speed is 300 r/min), wherein the reaction temperature of the saponification reaction is 80 ℃, and the reaction time is 4 hours;
(2) acidification reaction
Adding excessive phosphoric acid into the soap solution obtained in the step (1) to carry out an acidification reaction to obtain a fatty acid crude solution;
in the step (2), an acidification reaction is carried out under the condition of stirring (the stirring speed is 200 revolutions per minute), the reaction temperature of the acidification reaction is 85 ℃, and the reaction time is 1 hour;
(3) washing with water
Pouring the crude fatty acid solution obtained in the step (2) into a water washing tank, adding water for washing, standing after the washing is finished, and separating the upper fatty acid layer from the lower fatty acid layer;
in the step (3), the washing method comprises the following steps: adding 1 time of water (80 deg.C) into the fatty acid crude liquid, heating under stirring, boiling, and stirring for 10 min; standing for 1 hour after the water washing is finished;
in the step (3), the washing is performed for 3 times, that is: washing and separating the fatty acid obtained after the first washing and separation for the second time, washing and separating the fatty acid obtained after the second washing and separation for the third time, and feeding the obtained fatty acid into the next working procedure;
(4) vacuum drying
Vacuum drying the fatty acid obtained in the step (3);
in the step (4), the fatty acid obtained in the step (3) is put into a closed tank, the vacuum degree in the closed tank is 100Pa through vacuumizing, and water contained in the fatty acid is removed through heating (the heating temperature adopted in vacuum drying is 85 ℃);
(5) esterification reaction
Mixing the fatty acid obtained in the step (4) with glycerol according to a molar ratio of 2.4:1, adding corn oil into the fatty acid and the glycerol, wherein the weight of the added corn oil is 6% of that of the fatty acid, and uniformly mixing the fatty acid, the glycerol and the corn oil to obtain a first mixed material; then adding the first mixed material into an immobilized enzyme column, and reacting for 4 hours at the temperature of 55 ℃;
in the step (5), 4 immobilized enzyme columns are provided, the volume of each immobilized enzyme column is 50L, 18kg of immobilized lipase is filled in each column, and the 4 columns are arranged side by side; the flow rate of the first mixed material in the immobilized enzyme column is 600L/h;
(6) molecular distillation
And (3) performing molecular distillation on the reaction product obtained in the step (5) by adopting a molecular distillation device under the conditions that the distillation temperature is 148 ℃ and the vacuum degree is 0.1Pa (when the molecular distillation is performed, the feeding amount of the molecular distillation is 200L/h), wherein the heavy component obtained by the molecular distillation is the needed edible oil diglyceride.
The preparation process of the edible oil diglyceride can also comprise the step (7) of circulating reaction: mixing the light component obtained by molecular distillation in the step (6) with a newly prepared first mixed material, wherein the weight of the newly prepared first mixed material is 4 times that of the light component, and performing molecular distillation again after esterification reaction on the obtained mixture; the reaction is circulated 18 times. The newly blended first mixed material is the first mixed material obtained by uniformly mixing the fatty acid, the glycerol and the corn oil according to the proportion in the step (3). The esterification reaction and the molecular distillation in the cyclic reaction in the step (7) were performed with reference to the step (5) and the step (6), respectively, except that the reaction time of the esterification reaction in the cyclic reaction was 3 hours. After 18 times of circulating reaction, the yield reaches 93.4 percent, and the content of diglyceride in the final product is 86.78 percent.
Example 3
In this embodiment, the preparation process of edible oil diglyceride includes the following steps:
(1) saponification reaction
Carrying out saponification reaction on sunflower seed oil serving as a raw material to obtain a soap solution;
in the step (1), water and sodium hydroxide are added into sunflower seed oil, the weight ratio of the water to the sunflower seed oil is 1:3, and the addition amount of the sodium hydroxide is 15% of the weight of the sunflower seed oil; carrying out saponification reaction under the condition of stirring (the stirring speed is 300 r/min), wherein the reaction temperature of the saponification reaction is 85 ℃, and the reaction time is 4 hours;
(2) acidification reaction
Adding excessive phosphoric acid into the soap solution obtained in the step (1) to carry out an acidification reaction to obtain a fatty acid crude solution;
in the step (2), an acidification reaction is carried out under the condition of stirring (the stirring speed is 300 revolutions per minute), the reaction temperature of the acidification reaction is 82 ℃, and the reaction time is 1 hour;
(3) washing with water
Pouring the crude fatty acid liquid obtained in the step (2) into a water washing tank, adding water for washing, standing after the washing is finished, and separating the upper fatty acid layer from the lower fatty acid layer;
in the step (3), the washing method comprises the following steps: adding 0.5 times of water (80 deg.C) into the fatty acid crude liquid, heating under stirring, boiling, and stirring for 20 min; standing for 0.5 hour after the water washing is finished;
in the step (3), the washing is performed for 3 times, that is: washing and separating the fatty acid obtained after the first washing and separation for the second time, washing and separating the fatty acid obtained after the second washing and separation for the third time, and feeding the obtained fatty acid into the next working procedure;
(4) vacuum drying
Vacuum drying the fatty acid obtained in the step (3);
in the step (4), the fatty acid obtained in the step (3) is put into a closed tank, the vacuum degree in the closed tank is 100Pa through vacuumizing, and water contained in the fatty acid is removed through heating (the heating temperature adopted in vacuum drying is 95 ℃);
(5) esterification reaction
Mixing the fatty acid obtained in the step (4) with glycerol according to a molar ratio of 2:1, adding sunflower seed oil into the fatty acid and the glycerol, wherein the weight of the added sunflower seed oil is 9% of that of the fatty acid, and uniformly mixing the fatty acid, the glycerol and the sunflower seed oil to obtain a first mixed material; then adding the first mixed material into an immobilized enzyme column, and reacting for 4 hours at the temperature of 55 ℃;
in the step (5), 4 immobilized enzyme columns are provided, the volume of each immobilized enzyme column is 50L, 15kg of immobilized lipase is filled in each column, and the 4 columns are arranged side by side; the flow rate of the first mixed material in the immobilized enzyme column is 500L/h;
(6) molecular distillation
And (3) performing molecular distillation on the reaction product obtained in the step (5) by adopting a molecular distillation device under the conditions of the distillation temperature of 155 ℃ and the vacuum degree of 0.1Pa (when the molecular distillation is performed, the feeding amount of the molecular distillation is 200L/h), wherein the heavy component obtained by the molecular distillation is the needed edible oil diglyceride.
The preparation process of the edible oil diglyceride can also comprise the step (7) of circulating reaction: mixing the light component obtained by molecular distillation in the step (6) with a newly prepared first mixed material, wherein the weight of the newly prepared first mixed material is 5 times that of the light component, and performing molecular distillation again after esterification reaction on the obtained mixture; the reaction is circulated for 25 times. The newly blended first mixed material is obtained by uniformly mixing fatty acid, glycerol and sunflower seed oil according to the proportion in the step (3). The esterification reaction and the molecular distillation in the cyclic reaction in the step (7) were carried out with reference to the step (5) and the step (6), respectively, except that the reaction time of the esterification reaction in the cyclic reaction was 3.5 hours. After the circulation reaction is carried out for 25 times, the yield reaches 94.1 percent, and the content of diglyceride in the final product is 84.69 percent.
The invention relates to a method for measuring the content of monoglyceride, diglyceride and triglyceride, which comprises the following steps: the sample composition was analyzed by normal phase high performance liquid chromatography (NP-HPLC) using a high performance liquid chromatograph with a Waters 600 pump (Waters corporation, USA) equipped with a 2487 type UV detector (Waters corporation, USA). The column was a Lichrosorb Si-60 silica gel column (250X 4.6 mm, 5 μm, Grace, USA). Mobile phase a (n-hexane/isopropanol =99:1, V/V), mobile phase B (isopropanol), gradient elution conditions: 0-35 min, 100% A; 36-55 min, 80% A and 20% B; 56-65 min, 100% A. The elution flow rate was 1.0 m L/min, and the detection wavelength of the UV detector was 210 nm. After dissolving the sample in n-hexane, the sample is filtered by a 0.45 mu m organic membrane and then injected, and the injection volume is 20 mu L. And calculating the content of each glyceride component in the sample according to the standard curve of the standard substance.
Yield = final product/total amount of added edible oil x 100% (by weight). The total amount of the added edible oil is the sum of the edible oil added in the step (1), the step (5) and the step (7). The end product is the sum of the heavy components obtained after each molecular distillation.
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