CN115197776A - Refining process for reducing chloropropanol ester and glycidyl ester in vegetable oil by enzyme method - Google Patents
Refining process for reducing chloropropanol ester and glycidyl ester in vegetable oil by enzyme method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/003—Refining fats or fatty oils by enzymes or microorganisms, living or dead
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/008—Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/02—Refining fats or fatty oils by chemical reaction
- C11B3/06—Refining fats or fatty oils by chemical reaction with bases
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/10—Refining fats or fatty oils by adsorption
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Abstract
The invention belongs to the technical field of oil refining processing, and discloses a refining process for reducing chloropropanol ester and glycidyl ester in vegetable oil by an enzyme method, which comprises the following steps: degumming vegetable crude oil to obtain degummed oil, adding water and monoglyceride lipase, performing hydrolysis reaction to obtain degummed oil with low monoglyceride content, and performing alkali refining deacidification, decolorization and deodorization treatment to obtain edible vegetable oil with low chloropropanol ester and glycidyl ester content, wherein the addition amount of the monoglyceride lipase is 0.05-7.5wt% of the degummed oil, and the hydrolysis reaction time is 2-12h. The yield of the edible vegetable oil is higher than 95%, the GE content in the product is lower than 1.0mg/kg, the 3-MCPDE content in the product is lower than 1.25mg/kg, the limit regulation of the latest regulation of European Union is met, the removal rates of GE and 3-MCPDE respectively reach 86.52% and 83.19%, and the edible vegetable oil has great popularization value.
Description
Technical Field
The invention belongs to a refining processing technology of vegetable oil, and particularly relates to a refining process for reducing chloropropanol ester and glycidyl ester in vegetable oil by an enzymatic method.
Background
Glycidyl fatty acid ester is a general name of a compound formed by removing a molecule of water from two adjacent hydroxyl groups of glycerol to form an epoxy ring and esterifying the hydroxyl groups on the rest carbon with fatty acid, namely Glycidyl ester (abbreviated as GE or GEs), GEs are novel potential carcinogens discovered in oil products in recent years, products of the Glycidyl ester are glycidol under the hydrolysis action of lipase in human bodies, and are accumulated in human kidney tissues and other parts to cause tumors, the Glycidyl ester is listed as a 2A grade carcinogen by International cancer Institute (IARC) at present, and the chemical structural formulas of the Glycidyl ester and the Glycidyl ester are shown as formula 1. The chloropropanol ester comprises 3-chloropropanol ester, 2-chloropropanol ester and dichloropropanol ester, wherein 3-chloropropanol fatty acid ester (3-monochloro propane fatty acid esters, which are abbreviated as 3-MCPDE or 3-MCPDES) is a general name of a compound formed by substituting one terminal hydroxyl group on glycerol with a chlorine atom and esterifying the remaining one or two hydroxyl groups with fatty acid, because the relative content of the compound in vegetable oil is far higher than that of the other two, the 3-chloropropanol ester is usually used as a main monitoring index in edible oil, the generation condition of chloropropanol substances in the processing process of the edible oil can be reflected, and the chemical structural formula of the compound is shown as formula 2. In 2006, 3-chloropropanol ester was first discovered and disclosed. 3-chloropropanol esters have been classified by the International agency for research on cancer (IARC) as a "possible human carcinogen" category 2B.
Formula 1 glycidyl ester (left) and glycidyl ester (right) chemical structural formulas (R-is a non-carboxyl group of a fatty acid)
Formula 2 three 3-chloropropanol fatty acid esters of formula (R-is a non-carboxyl group of a fatty acid)
After the 3-MCPPDE and GEs in the edible oil are taken into a human body, the 3-MCPPDE and the GEs are hydrolyzed into 3-chloropropanol and glycidol with renal toxicity and genetic toxicity under the action of intestinal lipase. In 26 months 2 and 2018, the European Union firstly limits the GEs, the maximum limit of the GEs in the vegetable oil and fat is specified, the limit of the GEs in the food is not specified in other countries, regions and organizations, and China only limits the chloropropanol ester compounds in the product added with the acid hydrolysis vegetable protein. At present, the newly introduced regulation (EU) 2020/1322 of the European Union stipulates the sum of free 3-chloropropanol and 3-chloropropanol fatty acid ester in grease, and is implemented in No. 1/1 of 2021, and specific limiting parameters are shown in Table 1.
Table 1: european Commission Limited for GEs, 3-MCPD and 3-MCPPDE
Due to the defects of the traditional refining technology and the lack of specific limit measures for the GEs and the 3-MCPPDE, the domestic and foreign commercial vegetable oil is generally polluted by the GEs and the 3-MCPPDE, wherein the GEs and the 3-MCPPDE in the palm oil and the rice bran oil are seriously polluted, so the improvement of the oil processing and refining process to reduce the pollution of the GEs and the 3-MCPPDE is urgent.
Chinese patent application publication No. CN112725082A discloses a method for adsorbing pre-deodorized oil by using modified clay to obtain edible oil with low 3-chloropropanol ester and glycidyl ester contents. The method comprises the steps of firstly carrying out pre-deodorization treatment on oil at 180-220 ℃, then carrying out adsorption treatment on the oil by using modified argil, and finally carrying out deodorization treatment again at 220-250 ℃. The method needs two times of deodorization treatment, reduces yield, has complicated process and increases cost.
Chinese patent application publication No. CN112940853A discloses a method for reducing the content of free fatty acids, monoglycerides and diglycerides in oil to be deodorized by alkali refining deacidification and alcohol washing treatment. In the method, excessive alkali needs to be added in the alkali refining deacidification step, ethanol solution with the concentration of 70% or more needs to be added in the alcohol treatment step, the adding amount is 3-5 times of that of the feed liquid, and the alcohol washing times are 1-3 times. The method adds excessive alkali to cause material loss and yield reduction, and simultaneously, the use of organic solvent causes cost increase.
In conclusion, the existing technology for removing glycidyl ester and chloropropanol ester in grease has the defects of complex process, high cost, limited effect, low grease yield, small application range and the like, so that the existing method cannot be met in actual production, and a refining process for preparing edible oil with low content of glycidyl ester and chloropropanol ester, which has the advantages of low cost, convenience in operation and wide application range, is urgently needed.
Disclosure of Invention
In order to make up the defects of the existing edible vegetable oil refining processing technology, the invention mainly aims to provide a refining process for reducing chloropropanol ester and glycidyl ester in vegetable oil by an enzyme method.
The invention also aims to provide the edible vegetable oil with low chloropropanol ester and glycidyl ester contents, which is prepared by the process.
The invention further aims to provide application of the edible vegetable oil with low chloropropanol ester and glycidyl ester contents.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a refining process for reducing chloropropanol ester and glycidyl ester in vegetable oil by an enzyme method comprises the following steps:
(1) Degumming crude vegetable oil to obtain degummed oil;
(2) Taking the degummed oil obtained in the step (1), adding a certain amount of water and monoglyceride lipase, and performing hydrolysis reaction under a stirring condition to obtain the degummed oil with low monoglyceride content, wherein the addition amount of the monoglyceride lipase is 0.05-7.5wt% of the degummed oil, and the hydrolysis reaction time is 2-12h;
(3) And (3) taking the degummed oil with low monoglyceride content in the step (2), and performing alkali refining deacidification, decoloration and deodorization treatment to obtain the edible vegetable oil with low chloropropanol ester and glycidyl ester contents.
Preferably, the monoglyceride Lipase in the step (2) is one or two of Lipase GMGL and Lipase GMCL-160-CoMGL.
Preferably, the monoglyceride content of the degummed oil with low monoglyceride content after the hydrolysis reaction in the step (2) is less than 100mg/kg.
Preferably, the monoglyceride lipase of step (2): water: the mass ratio of the degummed oil is (0.001-0.075): (0.01-2.0): 1; the hydrolysis reaction temperature is 30-60 ℃, the stirring speed is 200-1000rpm, the hydrolysis reaction time is 4-8 h, and the hydrolysis reaction is carried out under the protection of nitrogen or inert gas.
Preferably, the hydrolysis reaction in the step (2) is an atmospheric hydrolysis reaction.
Preferably, the monoglyceride lipase of step (2): water: the mass ratio of the degummed oil is (0.003-0.005): (0.05-1.0): 1; the inert gas is helium, argon or neon.
Preferably, activated carbon and activated clay are added in the decoloring process in the step (3), wherein the ratio of activated carbon: activated clay: the mass ratio of the low monoglyceride-containing degummed oil is (0.001-0.005): (0.005-0.02): 1, the decoloring temperature is 80-120 ℃, and the decoloring time is 30-90min.
Preferably, the crude vegetable oil in step (1) is one or a combination of two or more of crude rice bran oil, crude corn oil, crude palm oil, crude linseed oil, crude rapeseed oil, crude sunflower seed oil, crude tea seed oil, crude soybean oil, crude peanut oil, crude walnut oil and crude cottonseed oil.
Preferably, the temperature of the deodorization treatment in the step (3) is 200-250 ℃, the deodorization time is 60-180 min, and the vacuum degree of the deodorization treatment is 200-500Pa.
Preferably, the degumming treatment in step (1) is: adding water and citric acid into the crude vegetable oil, wherein the degumming temperature is 80-100 ℃, the degumming time is 30-120 min, and the water: citric acid: the mass ratio of the crude oil is (0.01-0.05): (0.001-0.01): 1;
preferably, the alkali refining deacidification in the step (3) is carried out according to a conventional process, and the specific method refers to the influence of acid value of crude corn oil and alkali refining deacidification on glyceride composition and 3-chloropropanol ester and glycidyl ester of the crude corn oil, which is published in China oil & fat 2020, volume 45 and phase 2 of Liuyulan.
Preferably, the monoglyceride Lipase GMCL-160-CoMGL in the step (2) is prepared by the method in CN 113481183A.
An edible vegetable oil with low chloropropanol ester and glycidyl ester contents.
Preferably, the edible vegetable oil with low chloropropanol ester and glycidyl ester content contains less than 1.25mg/kg of 3-chloropropanol ester and less than 1.0mg/kg of glycidyl ester.
The edible vegetable oil with low chloropropanol ester and glycidyl ester content is applied to daily cooking and baking products.
Preferably, the edible vegetable oil with low chloropropanol ester and glycidyl ester content can be used for household daily cooking modes such as frying, stir-frying, roasting, stewing, mixing and the like.
Preferably, the edible vegetable oil with low chloropropanol ester and glycidyl ester content can be used as oil for baking products such as bread, biscuits, cakes and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The process for preparing the edible vegetable oil with the low chloropropanol ester and the glycidyl ester does not relate to the traditional physical adsorption method, and reagent consumables are not wasted, so the cost is reduced. Meanwhile, the hydrolysis method directly uses the vegetable crude oil and the water as raw materials, and has the advantages of environmental friendliness, greenness, safety and simplicity in operation.
(2) The method creatively uses monoglyceride Lipase to hydrolyze monoglyceride in the vegetable crude oil, and utilizes Lipase GMCL-160-CoMGL to hydrolyze the vegetable crude oil, so as to remove trace precursor monoglyceride of glycidyl ester and chloropropanol ester in the vegetable crude oil, simultaneously, triglyceride and diglyceride in the vegetable crude oil cannot be lost, and the monoglyceride content in the oil after full hydrolysis is lower than 100mg/kg, so that the higher oil yield is kept in the subsequent conventional refining process, and the content of glycidyl ester and chloropropanol in edible vegetable oil is reduced.
(3) The yield of the refined edible vegetable oil of the product obtained by the method is higher than 95%, the content of glycidyl ester in the product is lower than 1.0mg/kg, the content of chloropropanol ester in the product is lower than 1.25mg/kg, the product meets the limit regulation of the content of the glycidyl ester and the chloropropanol ester in the edible vegetable oil in the regulation (EU) 2020/1322 newly released by the European Union, the removal rate of the glycidyl ester can reach 80.05-86.52%, and the removal rate of the chloropropanol ester can reach 79.05-83.19%, so the method has great popularization value.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Glycerol monoester Lipase GMCL-160-CoMGL is disclosed in a patent CN113481183A, a marine microorganism Lipase chimera, a construction method and an application thereof, and is prepared by referring to the method in CN 113481183A.
Crude rice bran oil, crude corn oil, crude palm oil, crude rapeseed oil and crude soybean oil are all purchased from some oil processing enterprises in Jiangxi.
Example 1
Adding the soybean crude oil subjected to conventional degumming treatment (the water addition amount in the conventional degumming treatment is 3% of the weight of the oil, the citric acid addition amount is 0.12% of the weight of the oil, the degumming temperature is 80 ℃, and the degumming time is 30 min), adding distilled water and monoglyceride Lipase GMCL-160-CoMGL, fully stirring to completely mix substances in the reaction vessel, introducing nitrogen to protect a reaction product, sealing the reaction vessel, controlling the temperature of a reaction system to be 40 ℃, and controlling the stirring speed to be 200rpm; wherein the addition amount of the water is 100% of the mass of the degummed crude soybean oil, and the addition amount of the monoglyceride Lipase GMCL-160-CoMGL is 0.5% of the mass of the degummed crude soybean oil.
After 6.0h of reaction, the hydrolysis reaction was terminated by stopping the stirring. Centrifuging a hydrolysate at 12000rpm for 10min, taking an upper oil phase, measuring the acid value, calculating the theoretical alkali addition amount, specifically referring to the influence of acid value of crude corn oil and alkali refining deacidification on glyceride composition and 3-chloropropanol ester and glycidyl ester of the crude corn oil in an article published by Liuyulan in volume 2 of 45 in 2020, obtaining deacidified oil, adding activated carbon and activated clay for adsorption decoloration, and performing suction filtration after decoloration to separate the activated clay and the activated carbon to obtain colorless decolored oil; wherein the adding amount of the activated carbon is 0.1 percent of the mass of the deacidified oil, the adding amount of the activated clay is 1.0 percent of the mass of the deacidified oil, the decolorizing temperature is controlled to be 90 ℃, the stirring speed is controlled to be 200rpm, and the decolorizing time is 60min.
Placing the colorless decolored oil in a deodorizer for deodorization treatment; wherein the deodorization temperature is controlled at 240 deg.C, the deodorization time is 120min, and the residual pressure of the deodorizer is controlled at 0.4KPa. After the deodorization is finished, the mass specific gravity of the finished oil and the degummed crude soybean oil is calculated to obtain the yield of the finished oil of 97.6%, and meanwhile, the determination of the glycidyl ester and the chloropropanol ester is carried out according to the method in AOCS Cd 29a-13, and the result shows that the content of the glycidyl ester and the chloropropanol ester after the crude soybean oil is refined is 0.87 +/-0.12 mg/kg, and the content of the chloropropanol ester is 1.08 +/-0.09 mg/kg, and compared with the comparative example 1, the removal rates of the glycidyl ester and the chloropropanol ester respectively reach 80.05% and 79.11%.
Example 2
Adding conventional degummed crude rice bran oil (the water added in the conventional degummed treatment is 3% of the weight of the oil, the citric acid added is 0.12% of the weight of the oil, the degummed temperature is 80 ℃, and the degummed time is 30 min), adding distilled water and Lipase GMCL-160-CoMGL, fully stirring to completely mix substances in the reaction vessel, introducing nitrogen to protect a reaction product, sealing the reaction vessel, controlling the temperature of a reaction system to be 40 ℃, and controlling the stirring speed to be 200rpm; wherein the addition amount of the water is 100% of the mass of the degummed rice bran crude oil, and the addition amount of the monoglyceride Lipase GMCL-160-CoMGL is 0.5% of the mass of the degummed rice bran crude oil.
After 6.0h of reaction, the hydrolysis reaction was terminated by stopping the stirring. Centrifuging a hydrolysate at 12000rpm for 10min, taking an upper oil phase, measuring the acid value, calculating the theoretical alkali addition amount, specifically referring to the influence of acid value of crude corn oil and alkali refining deacidification on glyceride composition and 3-chloropropanol ester and glycidyl ester of the crude corn oil in an article published by Liuyulan in volume 2 of 45 in 2020, obtaining deacidified oil, adding activated carbon and activated clay for adsorption decoloration, and performing suction filtration after decoloration to separate the activated clay and the activated carbon to obtain colorless decolored oil; wherein the adding amount of the activated carbon is 0.1 percent of the mass of the deacidified oil, the adding amount of the activated clay is 1.0 percent of the mass of the deacidified oil, the decolorizing temperature is controlled to be 80 ℃, the stirring speed is controlled to be 200rpm, and the decolorizing time is 60min.
Deodorizing the colorless decolorized oil in a deodorizer; wherein the deodorization temperature is controlled at 220 deg.C, the deodorization time is 120min, and the residual pressure of the deodorizer is controlled at 0.4KPa. After the deodorization is finished, the mass specific gravity of the finished oil and the degummed crude rice bran oil is calculated to obtain the yield of the finished oil of 96.8%, and meanwhile, the determination of the glycidyl ester and the chloropropanol ester is carried out according to the method in AOCS Cd 29a-13, and the result shows that the content of the glycidyl ester and the chloropropanol ester in the refined crude rice bran oil are 0.79 +/-0.15 mg/kg and 0.97 +/-0.14 mg/kg, and compared with the comparative example 2, the removal rates of the glycidyl ester and the chloropropanol ester respectively reach 86.52% and 83.19%.
Example 3
Adding conventional degummed olive crude oil (the water added in the conventional degummed olive crude oil accounts for 3% of the weight of the oil, the citric acid added accounts for 0.12% of the weight of the oil, the degummed temperature is 80 ℃, the degummed time is 30 min), adding distilled water and monoglyceride Lipase GMCL-160-CoMGL, fully stirring to completely mix substances in the reaction vessel, introducing nitrogen to protect reaction products, sealing the reaction vessel, controlling the temperature of a reaction system to be 45 ℃, and controlling the stirring speed to be 200rpm; wherein the addition amount of the water is 70% of the mass of the degummed olive crude oil, and the addition amount of the monoglyceride Lipase GMCL-160-CoMGL is 0.5% of the mass of the degummed olive crude oil.
After 6.0h of reaction, the hydrolysis reaction was terminated by stopping the stirring. Centrifuging a hydrolysate at 12000rpm for 10min, taking an upper oil phase, measuring acid value, calculating theoretical alkali addition amount, specifically referring to the influence of acid value and alkali refining deacidification of corn crude oil on glyceride composition and 3-chloropropanol ester and glycidyl ester of the corn crude oil, namely, the influence of alkali refining deacidification on glyceride composition and 3-chloropropanol ester and glycidyl ester of the corn crude oil, which is published by Liuyulan in volume 2 of 45 in 2020, adding activated carbon and activated clay for adsorption decoloration, and performing suction filtration to separate the activated clay and the activated carbon after decoloration is finished to obtain colorless decolored oil; wherein the adding amount of the activated carbon is 0.1 percent of the mass of the deacidified oil, the adding amount of the activated clay is 1.0 percent of the mass of the deacidified oil, the decolorizing temperature is controlled to be 80 ℃, the stirring speed is controlled to be 200rpm, and the decolorizing time is 60min.
Deodorizing the colorless decolorized oil in a deodorizer; wherein the deodorization temperature is controlled at 220 deg.C, the deodorization time is 120min, and the residual pressure of the deodorizer is controlled at 0.4KPa. And after deodorization is finished, calculating the mass specific gravity of the finished oil and the degummed olive crude oil to obtain the yield of the finished oil of 96.8%, and simultaneously determining glycidyl ester and chloropropanol ester according to the method in AOCS Cd 29a-13, wherein the result shows that the content of the glycidyl ester is 0.88 +/-0.15 mg/kg and the content of the chloropropanol ester is 0.75 +/-0.14 mg/kg after the refining treatment of the olive crude oil.
Example 4
Adding palm crude oil subjected to conventional degumming treatment (the water added in the conventional degumming treatment is 3% of the weight of the oil, the citric acid added is 0.12% of the weight of the oil, the degumming temperature is 80 ℃, and the degumming time is 30 min), adding distilled water and monoglyceride Lipase GMCL-160-CoMGL, fully stirring to completely mix substances in the reaction vessel, introducing nitrogen to protect a reaction product, sealing the reaction vessel, controlling the temperature of a reaction system to be 40 ℃, and stirring at the speed of 200rpm; wherein the addition amount of the water is 80% of the mass of the degummed palm crude oil, and the addition amount of the monoglyceride Lipase GMCL-160-CoMGL is 0.4% of the mass of the degummed palm crude oil.
After 8.0h of reaction, the hydrolysis reaction was terminated by stopping the stirring. Centrifuging a hydrolysate at 12000rpm for 10min, taking an upper oil phase, measuring the acid value, calculating the theoretical alkali addition amount, specifically referring to the influence of acid value of crude corn oil and alkali refining deacidification on glyceride composition and 3-chloropropanol ester and glycidyl ester of the crude corn oil in an article published by Liuyulan in volume 2 of 45 in 2020, obtaining deacidified oil, adding activated carbon and activated clay for adsorption decoloration, and performing suction filtration after decoloration to separate the activated clay and the activated carbon to obtain colorless decolored oil; the method comprises the following steps of preparing the deacidified oil, adding activated carbon, activated clay and activated carbon into the deacidified oil, wherein the adding amount of the activated carbon is 0.1% of the quality of the deacidified oil, the adding amount of the activated clay is 1.0% of the quality of the deacidified oil, the decolorizing temperature is controlled to be 90 ℃, the stirring speed is controlled to be 200rpm, and the decolorizing time is 60min.
Placing the colorless decolored oil in a deodorizer for deodorization treatment; wherein the deodorization temperature is controlled at 240 deg.C, the deodorization time is 120min, and the residual pressure of the deodorizer is controlled at 0.4KPa. After the deodorization is finished, the mass specific gravity of the finished oil and the crude palm oil is calculated to obtain the yield of the finished oil of 96.9%, and meanwhile, the determination of the glycidyl ester and the chloropropanol ester is carried out according to the method in AOCS Cd 29a-13, and the result shows that the content of the glycidyl ester is 0.89 +/-0.06 mg/kg and the content of the chloropropanol ester is 1.15 +/-0.08 mg/kg after the crude palm oil is refined, and compared with the comparative example 3, the removal rates of the glycidyl ester and the chloropropanol ester respectively reach 80.31% and 79.05%.
Example 5
Adding the corn crude oil subjected to conventional degumming treatment (the water added in the conventional degumming treatment is 3% of the weight of the oil, the citric acid added is 0.12% of the weight of the oil, the degumming temperature is 80 ℃, and the degumming time is 30 min), adding distilled water and Lipase GMCL-160-CoMGL, fully stirring to completely mix substances in the reaction vessel, introducing nitrogen to protect a reaction product, sealing the reaction vessel, controlling the temperature of a reaction system to be 45 ℃, and controlling the stirring speed to be 200rpm; wherein the addition amount of the water is 50% of the mass of the degummed corn crude oil, and the addition amount of the monoglyceride Lipase GMCL-160-CoMGL is 0.3% of the mass of the degummed corn crude oil.
After 6.0h of reaction, the hydrolysis reaction was terminated by stopping the stirring. Centrifuging a hydrolysate at 12000rpm for 10min, taking an upper oil phase, measuring acid value, calculating theoretical alkali addition amount, specifically referring to the influence of acid value and alkali refining deacidification of corn crude oil on glyceride composition and 3-chloropropanol ester and glycidyl ester of the corn crude oil, namely, the influence of alkali refining deacidification on glyceride composition and 3-chloropropanol ester and glycidyl ester of the corn crude oil, which is published by Liuyulan in volume 2 of 45 in 2020, adding activated carbon and activated clay for adsorption decoloration, and performing suction filtration to separate the activated clay and the activated carbon after decoloration is finished to obtain colorless decolored oil; wherein the adding amount of the activated carbon is 0.1 percent of the mass of the deacidified oil, the adding amount of the activated clay is 1.0 percent of the mass of the deacidified oil, the decolorizing temperature is controlled to be 80 ℃, the stirring speed is controlled to be 200rpm, and the decolorizing time is 60min.
Deodorizing the colorless decolorized oil in a deodorizer; wherein the deodorization temperature is controlled at 250 deg.C, the deodorization time is 90min, and the residual pressure of the deodorizer is controlled at 0.4KPa. After the deodorization is finished, calculating the mass specific gravity of the finished oil and the crude corn oil to obtain the yield of the finished oil of 98.2%, and simultaneously determining glycidyl ester and chloropropanol ester according to the method in AOCS Cd 29a-13, wherein the result shows that the content of the glycidyl ester is 0.79 +/-0.07 mg/kg and the content of the chloropropanol ester is 1.08 +/-0.15 mg/kg after the crude corn oil is refined.
Example 6
Adding rapeseed crude oil subjected to conventional degumming treatment (the water added in the conventional degumming treatment is 3% of the weight of the oil, the citric acid added in the conventional degumming treatment is 0.12% of the weight of the oil, the degumming temperature is 80 ℃, and the degumming time is 30 min), adding distilled water and monoglyceride Lipase GMCL-160-CoMGL, fully stirring to completely mix substances in the reaction vessel, introducing nitrogen to protect a reaction product, sealing the reaction vessel, controlling the temperature of a reaction system to be 40 ℃, and stirring at the speed of 200rpm; wherein the addition amount of the water is 50% of the mass of the degummed crude rapeseed oil, and the addition amount of the monoglyceride Lipase GMCL-160-CoMGL is 0.3% of the mass of the degummed crude rapeseed oil.
After 6.0h of reaction, the hydrolysis reaction was terminated by stopping the stirring. Centrifuging a hydrolysate at 12000rpm for 10min, taking an upper oil phase, measuring the acid value, calculating the theoretical alkali addition amount, specifically referring to the influence of acid value of crude corn oil and alkali refining deacidification on glyceride composition and 3-chloropropanol ester and glycidyl ester of the crude corn oil in an article published by Liuyulan in volume 2 of 45 in 2020, obtaining deacidified oil, adding activated carbon and activated clay for adsorption decoloration, and performing suction filtration after decoloration to separate the activated clay and the activated carbon to obtain colorless decolored oil; wherein the adding amount of the activated carbon is 0.1 percent of the mass of the deacidified oil, the adding amount of the activated clay is 1.0 percent of the mass of the deacidified oil, the decolorizing temperature is controlled to be 90 ℃, the stirring speed is controlled to be 200rpm, and the decolorizing time is 60min.
Deodorizing the colorless decolorized oil in a deodorizer; wherein the deodorization temperature is controlled at 240 deg.C, the deodorization time is 120min, and the residual pressure of the deodorizer is controlled at 0.4KPa. After the deodorization is finished, calculating the mass specific gravity of the finished oil and the crude rapeseed oil to obtain the yield of the finished oil of 98.4%, and simultaneously determining glycidyl ester and chloropropanol ester according to the method in AOCS Cd 29a-13, wherein the result shows that the content of the glycidyl ester is 0.49 +/-0.10 mg/kg and the content of the chloropropanol ester is 0.97 +/-0.12 mg/kg after the crude rapeseed oil is refined.
Comparative example 1
Carrying out conventional degumming treatment on soybean crude oil, measuring acid value after degumming, calculating theoretical alkali addition amount, specifically referring to the article of the acid value of the corn crude oil and the influence of alkali refining deacidification on glyceride composition and 3-chloropropanol ester and glycidyl ester of the corn crude oil published by Liuyulan in volume 2 of 45 in 2020 of Chinese oil, adding 0.1% of activated carbon and 1% of activated clay (based on oil weight) for adsorption decoloration, and carrying out suction filtration after decoloration is finished to separate the clay and the activated carbon to obtain colorless decolored oil; the method comprises the following steps of preparing the deacidified oil, adding activated carbon, clay and water, wherein the adding amount of the activated carbon is 0.1% of the mass of the deacidified oil, the adding amount of the clay is 1.0% of the mass of the deacidified oil, the decoloring temperature is controlled to be 90 ℃, the stirring speed is controlled to be 200rpm, the decoloring time is 60min, the adding amount of water in the conventional degumming treatment is 3% of the weight of the oil, the adding amount of the citric acid is 0.12% of the weight of the oil, the degumming temperature is 80 ℃, and the degumming time is 30min.
Deodorizing the colorless decolorized oil in a deodorizer; wherein the deodorization temperature is controlled at 240 deg.C, the deodorization time is 120min, and the residual pressure of the deodorizer is controlled at 0.4KPa. After the deodorization is finished, calculating the mass specific gravity of the finished oil and the degummed crude soybean oil to obtain the finished oil with the yield of 98.2%, and simultaneously, measuring glycidyl ester and chloropropanol ester according to the method in AOCS Cd 29a-13, wherein the result shows that the content of the glycidyl ester is 4.36 +/-0.29 mg/kg and the content of the chloropropanol ester is 5.17 +/-0.35 mg/kg after the crude soybean oil is refined.
Comparative example 2
Adding rice bran crude oil subjected to conventional degumming treatment (the added water amount in the conventional degumming treatment is 3% of the weight of the oil, the added citric acid amount is 0.12% of the weight of the oil, the degumming temperature is 80 ℃, the degumming time is 30 min), measuring the acid value, calculating the theoretical alkali addition amount, and specifically, referring to the article ' the influence of the acid value of the crude corn oil and the alkali refining deacidification on the glyceride composition and the 3-chloropropanol ester and the glycidyl ester ' published in volume 2 of No. 45 of China grease ' of Liuyulan in 2020, adding activated carbon and activated clay for adsorption decoloration after obtaining deacidified oil, and performing suction filtration to separate the activated clay and the activated carbon after the decoloration is finished to obtain colorless decolored oil; wherein the adding amount of the activated carbon is 0.1 percent of the mass of the deacidified oil, the adding amount of the activated clay is 1.0 percent of the mass of the deacidified oil, the decolorizing temperature is controlled to be 80 ℃, the stirring speed is controlled to be 200rpm, and the decolorizing time is 60min.
Deodorizing the colorless decolorized oil in a deodorizer; wherein the deodorization temperature is controlled at 220 deg.C, the deodorization time is 120min, and the residual pressure of the deodorizer is controlled at 0.4KPa. After the deodorization is finished, calculating the mass specific gravity of the finished oil and the degummed crude rice bran oil to obtain the finished oil with the yield of 96.7%, and simultaneously, measuring glycidyl ester and chloropropanol ester according to the method in AOCS Cd 29a-13, wherein the result shows that the content of the glycidyl ester is 5.86 +/-0.42 mg/kg and the content of the chloropropanol ester is 5.77 +/-0.29 mg/kg after the crude rice bran oil is refined.
Comparative example 3
Adding crude palm oil subjected to conventional degumming treatment (the water added in the conventional degumming treatment is 3% of the weight of the oil, the citric acid added is 0.12% of the weight of the oil, the degumming temperature is 80 ℃, and the degumming time is 30 min), measuring the acid value, calculating the theoretical alkali added amount, and specifically referring to the influence of the acid value and alkali refining deacidification of the crude corn oil on the glyceride composition and 3-chloropropanol ester and glycidyl ester of the crude corn oil in the article published by Liuyulan in volume 45 and 2 of China oil & lt 2020 & gt, adding activated carbon and activated clay for adsorption decoloration after obtaining deacidified oil, and performing suction filtration after the decoloration is finished to separate the activated clay and the activated carbon to obtain colorless decolored oil; wherein the adding amount of the activated carbon is 0.1 percent of the mass of the deacidified oil, the adding amount of the activated clay is 1.0 percent of the mass of the deacidified oil, the decolorizing temperature is controlled to be 90 ℃, the stirring speed is controlled to be 200rpm, and the decolorizing time is 60min.
Deodorizing the colorless decolorized oil in a deodorizer; wherein the deodorization temperature is controlled at 240 deg.C, the deodorization time is 120min, and the residual pressure of the deodorizer is controlled at 0.4KPa. After the deodorization is finished, calculating the mass specific gravity of the finished oil and the crude palm oil to obtain the finished oil with the yield of 95.7%, and simultaneously determining glycidyl ester and chloropropanol ester according to the method in AOCS Cd 29a-13, wherein the result shows that the content of the glycidyl ester is 4.52 +/-0.19 mg/kg and the content of the chloropropanol ester is 5.49 +/-0.26 mg/kg after the crude palm oil is refined.
Comparative example 4
Adding the soybean crude oil subjected to conventional degumming treatment (the water added in the conventional degumming treatment is 3% of the weight of the oil, the citric acid added in the conventional degumming treatment is 0.12% of the weight of the oil, the degumming temperature is 80 ℃, and the degumming time is 30 min), adding distilled water and partial glyceride Lipase AOL, fully stirring to completely mix substances in the reaction vessel, introducing nitrogen to protect a reaction product, sealing the reaction vessel, controlling the temperature of a reaction system to be 40 ℃, and stirring at the speed of 200rpm; wherein the addition amount of the water is 100% of the mass of the degummed soybean crude oil, and the addition amount of the monoglyceride Lipase AOL is 0.5% of the mass of the degummed rice bran crude oil.
After 6.0h of reaction, the hydrolysis reaction was terminated by stopping the stirring. Centrifuging a hydrolysate at 12000rpm for 10min, taking an upper oil phase, measuring acid value, calculating theoretical alkali addition amount, specifically referring to the influence of acid value and alkali refining deacidification of corn crude oil on glyceride composition and 3-chloropropanol ester and glycidyl ester of the corn crude oil, namely, the influence of alkali refining deacidification on glyceride composition and 3-chloropropanol ester and glycidyl ester of the corn crude oil, which is published by Liuyulan in volume 2 of 45 in 2020, adding activated carbon and activated clay for adsorption decoloration, and performing suction filtration to separate the activated clay and the activated carbon after decoloration is finished to obtain colorless decolored oil; wherein the adding amount of the activated carbon is 0.1 percent of the mass of the deacidified oil, the adding amount of the activated clay is 1.0 percent of the mass of the deacidified oil, the decolorizing temperature is controlled to be 90 ℃, the stirring speed is controlled to be 200rpm, and the decolorizing time is 60min.
Deodorizing the colorless decolorized oil in a deodorizer; wherein the deodorization temperature is controlled at 240 deg.C, the deodorization time is 120min, and the residual pressure of the deodorizer is controlled at 0.4KPa. After deodorization is finished, the mass proportion of the finished oil and the degummed crude soybean oil is calculated, the yield of the finished oil is 87.6%, and the content of the glycidyl ester and the chloropropanol ester is measured according to the method in the AOCS Cd 29a-13, and the result shows that the content of the glycidyl ester is 1.72 +/-0.25 mg/kg and the content of the chloropropanol ester is 1.57 +/-0.28 mg/kg after the crude soybean oil is refined.
Comparative example 5
Adding conventional degummed olive crude oil (the water added in the conventional degummed treatment is 3% of the weight of the oil, the citric acid added is 0.12% of the weight of the oil, the degummed temperature is 80 ℃, and the degummed time is 30 min), adding distilled water and Lipase GMCL-160-CoMGL, fully stirring to completely mix substances in the reaction vessel, introducing nitrogen to protect a reaction product, sealing the reaction vessel, controlling the temperature of a reaction system to be 45 ℃, and controlling the stirring speed to be 200rpm; wherein the addition amount of the water is 70% of the mass of the degummed olive crude oil, and the addition amount of the monoglyceride Lipase GMCL-160-CoMGL is 0.5% of the mass of the degummed olive crude oil.
In contrast to example 3, the hydrolysis reaction was terminated after 1.0h of hydrolysis reaction by stopping the stirring. Centrifuging a hydrolysate at 12000rpm for 10min, taking an upper oil phase, measuring the acid value, calculating the theoretical alkali addition amount, specifically referring to the influence of acid value of crude corn oil and alkali refining deacidification on glyceride composition and 3-chloropropanol ester and glycidyl ester of the crude corn oil in an article published by Liuyulan in volume 2 of 45 in 2020, obtaining deacidified oil, adding activated carbon and activated clay for adsorption decoloration, and performing suction filtration after decoloration to separate the activated clay and the activated carbon to obtain colorless decolored oil; wherein the adding amount of the activated carbon is 0.1 percent of the mass of the deacidified oil, the adding amount of the activated clay is 1.0 percent of the mass of the deacidified oil, the decolorizing temperature is controlled to be 80 ℃, the stirring speed is controlled to be 200rpm, and the decolorizing time is 60min.
Placing the colorless decolored oil in a deodorizer for deodorization treatment; wherein the deodorization temperature is controlled at 220 deg.C, the deodorization time is 120min, and the residual pressure of the deodorizer is controlled at 0.4KPa. After the deodorization is finished, calculating the mass specific gravity of the finished oil and the degummed olive crude oil to obtain the finished oil with the yield of 98.7%, and simultaneously measuring glycidyl ester and chloropropanol ester according to the method in AOCS Cd 29a-13, wherein the result shows that the content of the glycidyl ester is 3.26 +/-0.33 mg/kg and the content of the chloropropanol ester is 4.36 +/-0.34 mg/kg after the refining treatment of the olive crude oil.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A refining process for reducing chloropropanol ester and glycidyl ester in vegetable oil by an enzyme method is characterized by comprising the following steps:
(1) Degumming crude vegetable oil to obtain degummed oil;
(2) Taking the degummed oil obtained in the step (1), adding a certain amount of water and monoglyceride lipase, and performing hydrolysis reaction under a stirring condition to obtain the degummed oil with low monoglyceride content, wherein the addition amount of the monoglyceride lipase is 0.05-7.5wt% of the degummed oil, and the hydrolysis reaction time is 2-12h;
(3) And (3) taking the degummed oil with low monoglyceride content in the step (2), and performing alkali refining deacidification, decoloration and deodorization treatment to obtain the edible vegetable oil with low chloropropanol ester and glycidyl ester contents.
2. The refining process for reducing chloropropanol ester and glycidyl ester in vegetable oil by using the enzyme method according to claim 1, wherein the monoglyceride Lipase in the step (2) is one or two of Lipase GMGL and Lipase GMCL-160-CoMGL.
3. The refining process for reducing chloropropanol ester and glycidyl ester in vegetable oil by using the enzyme method according to claim 1, wherein the monoglyceride content in the degummed oil with low monoglyceride content after the hydrolysis reaction in the step (2) is lower than 100mg/kg.
4. A refining process for enzymatic reduction of chloropropanol esters and glycidyl esters in vegetable oils according to claim 1, characterized in that the monoglyceride lipase of step (2): water: the mass ratio of the degummed oil is (0.001-0.075): (0.01-2.0): 1; and (3) the hydrolysis reaction temperature in the step (2) is 30-60 ℃, the stirring speed is 200-1000rpm, the hydrolysis reaction time is 4-8 h, and the hydrolysis reaction is carried out under the protection of nitrogen or inert gas.
5. A refining process for enzymatic reduction of chloropropanol esters and glycidyl esters in vegetable oils according to claim 4, characterized in that the monoglyceride lipase of step (2): water: the mass ratio of the degummed oil is (0.003-0.005): (0.05-1.0): 1; the inert gas is helium, argon or neon.
6. The refining process for reducing chloropropanol ester and glycidyl ester in vegetable oil by using the enzyme method according to any one of claims 1 to 5, characterized in that activated carbon and activated clay are added in the decoloring process in the step (3), wherein the activated carbon: activated clay: the mass ratio of the degummed oil with low monoglyceride content is (0.001-0.005): (0.005-0.02): 1, the decoloring temperature is 80-120 ℃, and the decoloring time is 30-90min.
7. The refining process for reducing chloropropanol ester and glycidyl ester in vegetable oil by the enzyme method according to claim 6, wherein the crude vegetable oil in step (1) is one or a combination of more than two of rice bran crude oil, corn crude oil, palm crude oil, linseed crude oil, rapeseed crude oil, sunflower seed crude oil, tea seed crude oil, soybean crude oil, peanut crude oil, walnut crude oil and cottonseed crude oil.
8. The refining process for reducing chloropropanol ester and glycidyl ester in vegetable oil by using the enzyme method according to claim 1, wherein the deodorization treatment temperature in the step (3) is 200-250 ℃, the deodorization time is 60-180 min, and the deodorization treatment vacuum degree is 200-500Pa.
9. An edible vegetable oil having a low chloropropanol ester and glycidyl ester content, obtainable by a process as claimed in any one of claims 1 to 8.
10. Use of the edible oil with low chloropropanol ester and glycidyl ester contents according to claim 9 in daily cooking and baking products.
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