CN113122382A - Preparation method of grease with low pollutant content - Google Patents

Preparation method of grease with low pollutant content Download PDF

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Publication number
CN113122382A
CN113122382A CN201911414624.7A CN201911414624A CN113122382A CN 113122382 A CN113122382 A CN 113122382A CN 201911414624 A CN201911414624 A CN 201911414624A CN 113122382 A CN113122382 A CN 113122382A
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oil
lipase
grease
content
reaction
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CN113122382B (en
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赵洋
张海
徐学兵
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Wilmar Shanghai Biotechnology Research and Development Center Co Ltd
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Wilmar Shanghai Biotechnology Research and Development Center Co Ltd
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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
    • 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
    • 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
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C11B3/04—Refining fats or fatty oils by chemical reaction with acids
    • 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
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C11B3/06—Refining fats or fatty oils by chemical reaction with bases

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Lubricants (AREA)
  • Fats And Perfumes (AREA)

Abstract

The invention provides a method for preparing grease with low pollutant content, which comprises the following steps: adding a citric acid solution into the grease for reaction, adding a sodium hydroxide/potassium hydroxide solution for reaction, adding water and lipase A for normal-pressure reaction, and adding lipase B for vacuum reaction. The method can be used for obtaining the grease with low phosphorus content, low acid value and low risk substance precursor. The method of the invention can obviously control and reduce the content of the pollutants in the final product, solve the problem of overhigh content of the pollutants in the grease and reduce the harm to human bodies.

Description

Preparation method of grease with low pollutant content
Technical Field
The invention belongs to the field of grease processing technology, and particularly relates to a method for controlling the content of various pollutants in grease.
Background
In recent years, the content of each pollutant of grease is more and more regarded by professionals and the public. A healthy grease is very important for the health of infants and adults.
Besides common phosphorus, soap, acid, peroxide, etc., contaminants to be considered include polycyclic aromatic hydrocarbons, plasticizers, 3-chloropropanol esters, glycidyl esters, etc. Wherein, the 3-chloro-1, 2-propanediol (3-MCPD) ester is an ester formed by connecting a single hydroxyl or two hydroxyls in the 3-chloro-1, 2-propanediol with a long-chain fatty acid. In recent years, researchers have found 3-chloropropanediol esters in many foods, such as bread, coffee, refined vegetable oils, baby milk powder, crackers, malt products, french fries, donuts, pickled olives and herrings. In 2008, 3-chloropropanediol ester was also detected in breast milk at a content of 300-. Considering the potential safety risks, the german food safety evaluation organization BfR postulates: during digestion in humans, 3-chloropropanol esters and glycidyl esters will hydrolyze to 100% to 3-chloropropanol and glycidol. This would be far in excess of safety standards, such as infant milk powder 12.5-20 times TDI (maximum daily intake), and adult vegetable fat 5-10 times TDI.
CVUA(Chemischen und
Figure BDA0002350868850000011
) The 3-chloropropanol ester content of common vegetable oil is roughly classified, wherein the 3-chloropropanol ester content of refined soybean oil and corn oil is lower than 2ppm, and the 3-chloropropanol ester content of hydrogenated oil and refined palm oil is higher than 4ppm and is defined as high content.
The industry has carried out a great deal of research on the method, has obtained some achievements, and has proposed an optimization scheme, which mainly comprises the following two methods: the first is to optimize the main refining sections of degumming, alkali refining, decoloring, deodorizing and the like; the second type is post-treatment of refined fats and oils, for example by physical adsorption.
The existing optimized processes and post-treatment methods have certain limitations and high cost, so that improvement on the prior art is needed to overcome the defects of the prior art.
Disclosure of Invention
The invention provides a grease treatment method, which comprises the following steps:
(1) carrying out normal pressure reaction in a reaction system containing the grease, water and lipase A, and stopping the normal pressure reaction when the acid value of the grease is increased by 2-10 mgKOH/g; and
(2) adding lipase B into the reaction system in the step (1) to carry out vacuum reaction, and stopping the vacuum reaction when the acid value of the grease is reduced to below 1 mgKOH/g;
wherein the lipase A is a lipase from Penniclium camembertii, and the lipase B is a lipase from Candida antarctica.
In one or more embodiments, the amount of water in the reaction system is 1 to 10 wt%, preferably 3 to 5 wt% based on the weight of the oil.
In one or more embodiments, the amount of lipase A in the reaction system is 10 to 50ppm, preferably 20 to 40ppm, based on the weight of the oil.
In one or more embodiments, lipase a is lipase G50.
In one or more embodiments, the atmospheric reaction is stopped until the acid value of the oil or fat increases by 3 to 8 mgKOH/g.
In one or more embodiments, in step (1), the reaction temperature is in the range of 40 to 80 ℃, preferably 45 to 65 ℃.
In one or more embodiments, the amount of lipase B in the reaction system is 1 to 5 wt%, preferably 2 to 4 wt% based on the weight of the oil.
In one or more embodiments, lipase B is selected from lipase CALB and lipase 453.
In one or more embodiments, in step (2), the vacuum reaction is stopped when the reaction reaches an acid value of the fats and oils of 0.3 to 1 mgKOH/g.
In one or more embodiments, in step (2), the reaction temperature is in the range of 40 to 80 ℃, preferably 45 to 65 ℃.
In one or more embodiments, in step (2), the vacuum is in the range of from 10 to 100 mbar.
In one or more embodiments, the method further comprises an acid-base reaction step performed prior to step (1), wherein the acid-base reaction step comprises: adding a citric acid solution into the grease, reacting for more than 10 minutes, and then adding an alkali liquor, and reacting for more than 5 minutes; wherein the addition amount of the citric acid is 500-2000ppm of the weight of the oil, and the amount of the alkali substance is 1-6 times of that of the citric acid.
In one or more embodiments, the acid-base reaction is carried out at a reaction temperature of 40 to 80 ℃, preferably 45 to 65 ℃.
In one or more embodiments, the citric acid solution has a concentration of 30 to 80 wt%, preferably 40 to 60 wt%.
In one or more embodiments, citric acid is added in an amount of 500-1000 ppm.
In one or more embodiments, the lye is a sodium hydroxide solution or a potassium hydroxide solution; the concentration of the sodium hydroxide solution or potassium hydroxide solution is preferably 5 to 20% by weight, more preferably 10 to 15% by weight.
In one or more embodiments, the amount of the substance of base is 2-4 times the amount of the substance of citric acid.
In one or more embodiments, the method further comprises one or more steps of water washing and drying, degumming, deacidifying, alkali refining, soaping, dewaxing, decoloring and deodorizing the grease after the vacuum reaction.
In one or more embodiments, the method further comprises water washing, drying and deodorizing the grease after the vacuum reaction.
The invention also provides grease prepared by the method of any embodiment of the invention.
In one or more embodiments, the grease has one or more of the following characteristics:
(1) the phospholipid content of the oil is less than 10ppm, preferably less than 5 ppm;
(2) the acid value of the oil is lower than 2mgKOH/g, preferably lower than 1 mgKOH/g;
(3) the content of 3-chloro-1, 2-propylene glycol ester in the grease is lower than 2mg/kg, preferably lower than 1 mg/kg; and
(4) the glycidyl ester content of the fat and oil is less than 5mg/kg, preferably less than 2 mg/kg.
The invention also provides an oil composition, wherein at least one oil in the oil composition is prepared by the method according to any embodiment of the invention.
In one or more embodiments, the fat or fat composition has one or more of the following characteristics: (1) the phospholipid content of the oil is less than 10ppm, preferably less than 5 ppm;
(2) the acid value of the oil is lower than 2mgKOH/g, preferably lower than 1 mgKOH/g;
(3) the content of 3-chloro-1, 2-propylene glycol ester in the grease is lower than 2mg/kg, preferably lower than 1 mg/kg; and
(4) the glycidyl ester content of the fat and oil is less than 5mg/kg, preferably less than 2 mg/kg.
The invention also provides the application of the lipase A and the lipase B in reducing the content of the oil pollutants, or the application in preparing the oil with reduced content of the oil pollutants; wherein the lipase A is a lipase from Penniclium camembertii, and the lipase B is a lipase from Candida antarctica.
In one or more embodiments, the use comprises: adding water and lipase A into oil and fat, carrying out normal pressure reaction, stopping normal pressure reaction when the acid value of the oil and fat is increased by 2-10mgKOH/g, adding lipase B, carrying out vacuum reaction, and stopping vacuum reaction when the acid value of the oil and fat is reduced to below 1 mgKOH/g.
The invention also provides application of the method in any embodiment of the invention in reducing the phospholipid content, the acid value, the 3-MCPD ester content and/or the GE content of the grease.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range. Herein, unless otherwise specified, percentages refer to mass percentages and ratios to mass ratios.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
In this context, the starting materials mentioned may, unless otherwise indicated, be those conventional in the art, and the processes mentioned may be those conventionally carried out in the art, as reasonably determined by the skilled person from the disclosure and the prior art.
The invention aims to solve the technical problem of providing a brand-new grease pretreatment process, which can effectively control the content of each pollutant in a grease final product and is suitable for the industrial production of grease.
Herein, the contaminants mainly include phospholipids, free fatty acids, 3-chloro-1, 2-propanediol (3-MCPD) esters, Glycidyl Esters (GE), and peroxides; the oil with low pollutant content is oil with low phosphorus content, low Acid Value (AV), low 3-MCPD ester content and/or low GE content; controlling/reducing the content of contaminants in the oil means controlling/reducing the phospholipid content, AV, 3-MCPD ester content and/or GE content of the oil.
The invention discovers that after a proper amount of citric acid solution (such as 500-2000ppm of the weight of oil) is added into the oil and reacted for a period of time, a proper amount of alkali liquor (such as 1-6 times of the amount of the alkali substance as the added citric acid substance) is added and reacted for a period of time, so that the phospholipid content of the oil and fat can be reduced, and the amount of 3-MCPD ester and GE generated when the obtained oil and fat undergo subsequent high-temperature deodorization is greatly reduced.
Accordingly, the present invention includes a method of treating grease comprising: adding a citric acid solution into the grease to ensure that the content of the citric acid in the grease reaches 500-2000ppm, and reacting for more than 10 minutes; then adding alkali liquor, wherein the amount of the added alkali is 1-6 times of that of the added citric acid, and reacting for more than 5 minutes. In general, in the step of adding the citric acid solution, the reaction time is 10 minutes to achieve the desired effect of the present invention, and thus the upper limit of the reaction time is not particularly limited and may be determined according to actual production conditions. For example, the range time in this step may be in the range of 10 to 60 minutes, more preferably 10 to 30 minutes. The time for the treatment with the alkali solution added is 5 minutes for the reaction to obtain the desired effect of the present invention, and therefore, similarly, the upper limit of the reaction time for the treatment is not particularly limited and can be determined according to the actual production conditions. For example, the range time in this step may be in the range of 5 to 30 minutes, more preferably 5 to 15 minutes.
In the present invention, the temperature of the reaction after addition of the citric acid solution and the reaction after addition of the alkali solution may be 40 to 80 deg.C, preferably 45 to 65 deg.C.
In the present invention, the concentration of the citric acid solution is not particularly limited, and may be, for example, 30 to 80 wt%, preferably 40 to 60 wt%. In some embodiments, citric acid solution is added into the grease to make the citric acid content in the grease reach 500-1000 ppm; preferably, a citric acid solution with a concentration of 40-60 wt% is added.
In the present invention, the alkali solution may be a sodium hydroxide solution or a potassium hydroxide solution. The concentration of the sodium hydroxide solution or potassium hydroxide solution is not particularly limited, and may be, for example, 5 to 20% by weight, preferably 10 to 15% by weight. In certain embodiments, the amount of base added is 2-4 times, e.g., 2.5-3.5 times, about 3 times, the amount of citric acid added; preferably, the lye added is a sodium hydroxide solution or a potassium hydroxide solution with a concentration of 10 to 15% by weight.
The invention finds that the acid value of the oil can be reduced by adding water and lipase A (lipase from Penniclilium camembertii) into the oil to carry out a normal pressure reaction, adding lipase B (lipase from Candida antarctica) to carry out a vacuum reaction when the acid value is increased by a certain value (for example, 2-10mgKOH/g) until the acid value is reduced to a certain value (for example, below 1 mgKOH/g), and the content of 3-MCPD ester and the amount of GE generated when the obtained oil is subjected to subsequent high-temperature deodorization are greatly reduced.
Accordingly, the present invention includes a method of treating grease comprising: adding water and lipase A into the grease to carry out normal pressure reaction, and stopping the normal pressure reaction when the acid value of the grease is increased by 2-10 mgKOH/g; adding lipase B, carrying out vacuum reaction, and stopping the vacuum reaction when the acid value of the grease is reduced to below 1 mgKOH/g; wherein lipase A is derived from Penniclilium camembertii, and lipase B is derived from Candida antarctica.
The "normal pressure reaction" in the present invention means that the reaction in a reaction system containing fat and oil, water and lipase a is carried out at normal pressure; the "vacuum reaction" in the present invention means that the reaction in the reaction system to which the lipase B is added is carried out under vacuum. In the present invention, the degree of vacuum of the vacuum reaction may be that of a conventional enzyme-catalyzed esterification reaction, and may be, for example, 10 to 100mbar, preferably 30 to 60 mbar. In the present invention, the operation of "reacting" means usually stirring and/or leaving the reaction system to stand unless otherwise specified.
The lipase A suitable for use in the present invention may be any of the various lipases from Penniclilium camembertii commonly used in the art, such as lipase G50. The lipase B suitable for use in the present invention may be any of various lipases derived from Candida antarctica (Candida antarctica) commonly used in the art, such as lipase CALB, lipase 453.
In the present invention, the temperature of the atmospheric reaction catalyzed by lipase A and the vacuum reaction catalyzed by lipase B may be 40 to 80 ℃ and preferably 45 to 65 ℃.
In the present invention, the amount of water added may be 1 to 10% by weight, for example, 1 to 8%, 1 to 5%, 1 to 4%, 2 to 4%, 3 to 10%, 3 to 8%, etc., based on the weight of the oil, and preferably 3 to 5%.
In the present invention, the amount of lipase A added may be 10 to 50ppm, preferably 20 to 40ppm, for example 25 to 35ppm, based on the weight of the oil.
In certain embodiments, the atmospheric reaction is stopped when the acid value of the oil or fat is increased by 2 to 8mgKOH/g, preferably 3 to 8mgKOH/g (e.g., 3 to 7mgKOH/g, 4 to 6mgKOH/g, 5 to 6 mgKOH/g).
In the present invention, the amount of lipase B added may be 1 to 5 wt%, preferably 2 to 4 wt%, for example 2.5 to 3.5 wt% based on the weight of the oil.
In certain embodiments, the vacuum reaction is stopped when the acid value of the oil or fat has dropped to 0.3 to 1mgKOH/g, preferably 0.3 to 0.8 mgKOH/g.
The invention discovers that the phospholipid content and the acid value of the oil can be reduced by jointly applying the oil treatment method, and the content of 3-MCPD ester and the amount of GE generated when the obtained oil is subjected to subsequent high-temperature deodorization are greatly reduced. The invention can simultaneously reduce the phospholipid content and AV of the grease together by the combined process of acid-base regulation and enzyme method combination of the grease system, does not generate soap, finally effectively controls the content of pollutants in the final product, and is not influenced by high-temperature deodorization.
Accordingly, the present invention also includes a method of treating a fat or oil comprising: adding a citric acid solution into the grease to ensure that the content of the citric acid in the grease reaches 500-2000ppm, and reacting for more than 10 minutes; then adding alkali liquor, wherein the amount of the added alkali is 1-6 times of that of the added citric acid, and reacting for more than 5 minutes; then adding water and lipase A, carrying out normal pressure reaction, stopping normal pressure reaction when the acid value of the grease is increased by 2-10mgKOH/g, preferably 3-8mgKOH/g, adding lipase B, carrying out vacuum reaction, and stopping vacuum reaction when the acid value of the grease is reduced to below 1 mgKOH/g; wherein lipase A is derived from Penniclilium camembertii, and lipase B is derived from Candida antarctica. The various process parameters in the fat treatment process may be as described in any of the embodiments herein.
The oil or fat to be used in the present invention is not particularly limited, and may be any of various oils or fats well known in the art, particularly edible oils including animal oils and fats, vegetable oils and fats, and algal oils and fats. Exemplary vegetable oils include, but are not limited to, rice oil, sunflower oil, palm kernel oil, peanut oil, rapeseed oil, cottonseed oil, safflower oil, perilla seed oil, tea seed oil, palm fruit oil, coconut oil, olive oil, cocoa butter, Chinese tallow seed oil, almond oil, tung seed oil, rubber seed oil, rice bran oil, corn germ oil, wheat germ oil, sesame seed oil, castor seed oil, linseed oil, evening primrose seed oil, hazelnut oil, walnut oil, grape seed oil, linseed oil, glass chicory seed oil, sea buckthorn seed oil, tomato seed oil, pumpkin seed oil, macadamia nut oil, cocoa butter, and the like, and any mixtures of two or more of these oils. Exemplary animal fat and oil can be one or more of beef tallow, lard, mutton fat, chicken fat, fish oil, seal oil, whale oil, dolphin oil, oyster oil, etc., or any mixture thereof. The oil and fat can be various oil and fat needing to control the content of pollutants, and can be crude oil, or the oil and fat (such as degummed oil, deacidified oil, alkali refining, soaped oil, dewaxed oil, decolored oil, deodorized oil and the like) refined by one-step or multi-step oil and fat refining processes (such as degumming, deacidification, alkali refining, soaped oil, dewaxed oil, decolored oil, deodorized oil, refined oil and the like). For example, the oil and fat treatment method of the present invention may be used to treat palm oil, coconut oil, and neutralized soybean oil. In some embodiments, the grease used in the process of the present invention is at least neutralized, i.e., the grease is a neutralized oil.
After the grease is treated by the grease treatment method, the treated grease can be optionally subjected to grease refining processes such as water washing drying, degumming, deacidification, alkali refining, soaping, dewaxing, decoloring, deodorization and the like. The oil refining processes suitable for the present invention, such as water washing drying, degumming, deacidification, alkali refining, soaping, dewaxing, decolorization, deodorization, etc., may be conventional in the art.
In the present invention, the degumming method may be a conventional degumming method in the art, and the specific process is well known to those skilled in the art, for example, but not limited to, the method in beret oil chemistry and technology (volume six), etc. Degumming may be enzymatic degumming or acid degumming. Typically, enzymatic degumming comprises: adding degumming enzyme (such as phospholipase) into oil, reacting for a period of time at certain temperature and pH, and separating colloid to obtain degummed oil. The enzymatic degumming temperature can be 40-60 ℃, and preferably 40-50 ℃; the pH may be from 4 to 6, preferably from 4.5 to 5.5; the reaction time can be 2-6h, preferably 3-5 h; the amount of enzyme added may be 5-1000mg/kg, preferably 10-100mg/kg, based on the weight of the oil. Typically, acid degumming comprises: adding acid solution into oil, stirring, performing solid-liquid separation, and collecting oil phase. Specifically, the acid refining degumming temperature can be 40-90 ℃, and preferably 50-70 ℃; the degumming time can be 10-60min, preferably 15-45 min; the acid solution may be a phosphoric acid solution and/or a citric acid solution, and may be, for example, a phosphoric acid solution having a concentration of 10 to 30 wt%, preferably 10 to 15 wt%; the amount of the acid solution to be used depends on the particular acid solution selected, and for example, when a phosphoric acid solution having a concentration of 10 to 15 wt% is used, the amount may be 0.1 to 1%, preferably 0.3 to 0.5% by mass of the fat; the solid-liquid separation method may be centrifugal separation.
The degumming may be followed by deacidification, the main purpose of which is to remove free fatty acids from the oils and fats, as well as to remove some of the impurities such as pigments, phospholipids, hydrocarbons and mucilage. The deacidification process may be conventional in the art. Physical deacidification methods may be used for deacidification. For example, the degummed oil may be treated at a pressure of 0.02 to 0.6kPa and a temperature of 180 ℃ and 250 ℃ to obtain a deacidified oil. Physical deacidification may be performed using a falling film evaporator. Deacidification can also be carried out by alkali refining (neutralization). The alkali refining method may be a method which is conventional in the art, and the specific process is well known to those skilled in the art, for example, but not limited to, the method in Belley oil chemistry and technology (volume six), etc. Typically, the caustic refining comprises: adding alkali liquor into the grease, and reacting for a period of time at a certain temperature. Specifically, the alkali refining temperature (temperature at which the fats and oils are reacted with the alkali solution) may be usually 40 to 90 ℃, preferably 40 to 85 ℃; the alkali refining reaction time may be usually 10 to 120min, for example, preferably 30 to 120 min; the lye is usually a sodium hydroxide solution, the concentration of which may be from 10 to 20% by weight, for example preferably from 3 to 15% by weight; the addition of lye may be conventional in the art and may be, for example, from 0.5 to 15%, from 1 to 10% by weight of the oil. As will be appreciated by those skilled in the art, the base added during caustic refining is divided into the theoretical basesAnd excess base. Usually, the amount of alkali added is 7.13X 10-4×MOilX AV x (1+ excess alkali), the excess alkali can be 0-20%, the alkali liquor amount is alkali addition amount/alkali liquor concentration, wherein, MOilOil weight, AV acid number. And (4) after the reaction of the alkali liquor and the grease is finished, centrifuging to obtain the neutralized oil.
The deacidification may be followed by water washing and drying to remove soap. The washing and drying method may be conventional in the art, and for example, the neutralized oil may be heated to 80-90 deg.C, washed with hot water in an amount of less than 5 wt% (e.g., 1-5 wt%, 1-3 wt%) of the oil, centrifuged, and vacuum dried at 90-120 deg.C to obtain the desquamated oil.
The methods of dewaxing may be conventional in the art. The dewaxing treatment can be carried out after degumming, after deacidification or after washing and drying. An exemplary process for dewaxing fats comprises pumping fats (such as degummed oil, deacidified oil, or soaped oil) into a crystallization tank, controlling the temperature to 50-60 ℃, standing for 10-60min, and then cooling for crystallization. Can be reduced to 0-6 deg.C (preferably 2-6 deg.C and 2-4 deg.C) within 10-60 hr, and then crystallized at the temperature for 6-10 hr, and filtering after crystallization is finished.
The decolorization method can be a conventional decolorization method in the art, and the specific process is well known to those skilled in the art, for example, but not limited to, the method in Belley oil chemistry and technology (volume six), etc. Typically, the decolorization includes: adding a proper amount of decolorizing agent into the grease, reacting at a certain temperature under vacuum condition, and filtering after reaction. Specifically, the decolorizing temperature can be 100-120 ℃, preferably 105-115 ℃; the addition amount of the decolorizing agent can be 0.5-5% of the grease mass, and is preferably 1-5%. The decolorizing agent can be any of a variety of decolorizing agents well known in the art including, but not limited to, kieselguhr, activated clay, activated carbon, zeolites, attapulgite, diatomaceous earth, silica gel, and the like. The degree of vacuum for the decolorization can be 20 to 100mbar, preferably 30 to 50 mbar. The decolorization time may be 20-120min, preferably 30-120 min.
The specific process of deodorization is well known to those skilled in the art, and for example, but not limited to, the method in Berea oil chemistry and technology (vol. sixth), etc. can be used. For example, deodorisation may include: introducing nitrogen or water vapor as deodorizing medium into oil, contacting oil with nitrogen or water vapor at certain temperature and vacuum degree for a certain period of time, and optionally deodorizing with falling film evaporator. The deodorization can be carried out under the conventional deodorization conditions in the field, and the deodorization temperature is preferably less than or equal to 280 ℃, such as 180-. The vacuum degree of deodorization is usually less than or equal to 25mbar, such as 1-10mbar and 1-5 mbar. The deodorization time may be 0.5-3h, preferably 1-2 h.
In certain embodiments, the method of treating fats and oils of the present invention comprises: washing and drying the grease treated by the grease treatment method described herein (for example, grease reacted with citric acid solution and alkali solution, grease subjected to normal pressure reaction under catalysis of lipase a and vacuum reaction under catalysis of lipase B after reaction with citric acid solution and alkali solution), and then deodorizing; the deodorization can be carried out at the temperature of 240 ℃ and 280 ℃, and the vacuum degree of the deodorization can be 1-5 mbar.
In a preferred embodiment, the method for treating fats and oils of the present invention comprises:
adding 30-80 wt% citric acid solution into the grease at 50-65 deg.C (the following reactions are all kept in the temperature range), so that the citric acid content in the grease reaches 500-2000ppm (preferably 500-1000ppm), stirring at constant temperature for more than 10min, then adding 5-20 wt% sodium hydroxide solution or potassium hydroxide solution, wherein the amount of the added sodium hydroxide or potassium hydroxide is 1-6 times (preferably 2-4 times) of the amount of the added citric acid, and reacting for more than 5 min; then adding 1-10% (preferably 3-5%) of water and 10-50ppm (for example 30 ppm) of lipase A (a lipase from Penniclium camembertii, such as lipase G50) to the oil to carry out a normal pressure reaction, adding 1-5% (for example 3%) of lipase B (a lipase from Candida antarctica, such as lipase CALB, lipase 453, etc.) to the oil to carry out a vacuum reaction when the acid value of the reaction system is increased by 3-8mgKOH/G (preferably 5-6mgKOH/G), and controlling the acid value of the oil at the end point of the reaction to be lower than 1mgKOH/G (for example 0.3-0.8 mgKOH/G); optionally, the grease obtained by the reaction is subjected to conventional water washing centrifugation, drying and deodorization.
After the grease is treated by the method, the grease can be optionally washed, centrifuged and separated by conventional water and dried to obtain the grease with low phosphorus content, low acid value and low risk substance precursor.
Herein, the risk substance precursor refers to a compound contained in the grease that is converted into 3-MCPD ester and GE during high temperature deodorization.
Accordingly, the present invention includes fats and oils produced by the fat and oil treatment method according to any of the embodiments herein.
The invention also includes a fat, which can be prepared by the fat treatment method described herein, and which has one or more of the following characteristics:
(1) the phosphorus content of the grease is less than 10ppm, preferably less than 5 ppm;
(2) the acid value of the oil is lower than 2mgKOH/g, preferably lower than 1 mgKOH/g;
(3) the content of 3-chloro-1, 2-propylene glycol ester in the grease is lower than 2mg/kg, preferably lower than 1 mg/kg; and
(4) the glycidyl ester content of the fat or oil is less than 5mg/kg, preferably less than 2mg/kg, more preferably less than 1.5 mg/kg.
The invention also includes a grease composition, wherein at least one grease in the grease composition is prepared by the grease treatment method, and preferably, the grease composition has one or more of the following characteristics:
(1) the phosphorus content of the grease is less than 10ppm, preferably less than 5 ppm;
(2) the acid value of the oil is lower than 2mgKOH/g, preferably lower than 1 mgKOH/g;
(3) the content of 3-chloro-1, 2-propylene glycol ester in the grease is lower than 2mg/kg, preferably lower than 1 mg/kg; and
(4) the glycidyl ester content of the fat or oil is less than 5mg/kg, preferably less than 2mg/kg, more preferably less than 1.5 mg/kg.
The invention also includes the use of lipase a and lipase B in the preparation of a low contaminant content fat, wherein lipase a is a lipase from penniclium camembertii and lipase B is a lipase from Candida antarctica (Candida antarctica). In the use of the present invention, lipase a and lipase B are as described in any of the embodiments herein, and the use may be to perform the treatment of fats and oils with lipase a and lipase B as described in any of the embodiments herein.
Compared with the prior art, the invention has the following advantages:
(1) compared with the normal refining process, the method has the advantages that the content of each pollutant in the final product is obviously reduced, and the influence of high-temperature deodorization is avoided;
(2) the invention belongs to a pretreatment means, can replace a degumming working section, does not generate soap, and does not influence the subsequent refining process of grease;
(3) compared with the existing post-treatment process, the process disclosed by the invention is low in difficulty, secondary processing is avoided, and the indexes of 3-MCPD ester, GE and AV of the grease finished product can be controlled at a low level at one time.
The following examples are further illustrative of the present invention, but the present invention is not limited to the following. The embodiments in the present description are only for illustrating the present invention, and do not limit the scope of the present invention. The scope of the present invention is defined only by the appended claims, and any omissions, substitutions, and changes in the form of the embodiments disclosed herein that may be made by those skilled in the art are intended to be included within the scope of the present invention.
The following examples use instrumentation conventional in the art. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. In the following examples, various starting materials were used, and unless otherwise specified, conventional commercially available products were used. In the description of the present invention and the following examples, "%" represents weight percent and "parts" represents parts by weight unless otherwise specified.
In the following examples and comparative examples, the oil of wool palm was obtained from PGEO factory, Malaysia, the phospholipid content was 58.2ppm, the acid value was 10.21mgKOH/g, and the pH was 4.48; lipase G50 and lipase 453 are from Novistin.
Detection methods of 3-MCPD and GE: with reference to ISO 18363-1 (equivalent to AOCS Cd 29c-13), the 3-MCPD and GE in the ester state were hydrolyzed to the free state using the basic transesterification method, and then derivatized with phenylboronic acid and detected by GC-MS.
The phosphorus content detection method comprises the following steps: and (3) testing the content of the phospholipid according to GB/T5537-2008 grain and oil.
The acid value detection method comprises the following steps: according to the determination of the acid value in the GB 5009.229-2016 food safety national standard food.
The first embodiment is as follows: influence of different process combinations on reduction of indexes
The grease of example 1-1 was prepared as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, and carrying out conventional water washing centrifugation and drying on the oil to obtain pretreated oil; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The preparation of the fats and oils of examples 1-2 was as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the grease to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the grease to reach 312ppm, reacting for more than 5min, and carrying out conventional water washing centrifugation and drying on the grease to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The preparation of the fats and oils of examples 1 to 3 was as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 13000ppm, reacting for more than 5min, and carrying out conventional water washing centrifugation and drying on the oil to obtain pretreated oil; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The preparation of the fats and oils of examples 1 to 4 was as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding 3% of distilled water and 30ppm of lipase G50 to carry out normal pressure reaction, adding 3% of lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain the pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The preparation of the fats and oils of examples 1 to 5 was as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is increased by 5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The preparation of the fats and oils of examples 1 to 6 was as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 3% of lipase 453 to perform vacuum reaction, and performing conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/g to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The preparation of the fats and oils of examples 1 to 7 was as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The pH, phospholipid content (P content), Acid Value (AV) and 3-chloropropanol ester (3-MCPD ester) content and Glycidyl Ester (GE) content of the final product of the process samples of examples 1-1 to 1-7 were measured, and the process parameters and performance test results for each proportion are summarized in tables 1 and 2.
Table 1: results of examining Process parameters and Properties in examples 1-1 to 1-7
Figure BDA0002350868850000151
Table 2: results of Performance test of examples 1-1 to 1-7
Figure BDA0002350868850000152
By comparing different process combinations, the invention unexpectedly discovers that the combined process of the single-purity citric acid and the sodium hydroxide at low temperature can effectively reduce the phosphorus content in the grease and the content of the 3-MCPD ester in the final product, but does not basically act on GE, but under specific conditions, by combining enzyme method, the phospholipid content and the acid value in the grease and the content of the 3-MCPD ester and GE in the final product can be simultaneously reduced by controlling the acid value of the grease to be increased and then decreased and controlling the increasing and decreasing amplitude of the acid value, and the amplitude is very obvious and the effect is better than that of the existing post-treatment modes (such as high-temperature alkali reaction and low-temperature refining).
By comparing examples 1-2 and 1-3, the present inventors have found that the combined process of citric acid and sodium hydroxide suitable for the present invention is different from the conventional alkali refining process in that the amount of sodium hydroxide added for the conventional alkali refining has no effect on the content control of 3-MCPD ester and GE, and brings about a large loss of neutral oil.
Example two: influence of different acid and alkali dosage on reduction of indexes
The grease of example 2-1 was prepared as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 104ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The grease of example 2-2 was prepared as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The preparation of the fats and oils of examples 2 to 3 was as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 626ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The preparation of the fats and oils of examples 2 to 4 was as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 1000ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 626ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The P content, acid value, and 3-MCPD ester content and GE content of the final product were determined for the process samples of examples 2-1 to 2-4, and the process parameters and performance measurements for each example are summarized in Table 3.
Table 3: results of examining Process parameters and Properties in examples 2-1 to 2-4
Figure BDA0002350868850000171
From the results of this example, it is found that the amount of alkali used directly affects the phospholipid content of the fat or oil. The more suitable addition amount of the alkali is 2-4 times, preferably about 3 times of the addition molar amount of the citric acid, the removal rate of the phospholipid is reduced when the addition amount is too small, the soap content in a system is increased when the addition amount is too large, the effect of the subsequent process is influenced, and the adverse effect is exerted on the content of the 3-MCPD ester serving as a final product.
Example three: influence of different distilled water addition amounts on reduction of various indexes
The grease of example 3-1 was prepared as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 1% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The grease of example 3-2 was prepared as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The preparation of the fats and oils of examples 3-3 was as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 5% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The preparation of the fats and oils of examples 3 to 4 was as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 10% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The P content, acid value, and 3-MCPD ester content and GE content of the final product were determined for the process samples of examples 3-1 to 3-4, and the process parameters and performance measurements for each example are summarized in Table 4.
Table 4: results of examining Process parameters and Properties in examples 3-1 to 3-4
Figure BDA0002350868850000191
From the results of this example, it is understood that an increase in the amount of water added is beneficial for the control of phospholipids and 3-MCPD esters, and that a preferred amount of water added is 3% to 5%, and when it exceeds 5%, it is adversely affected and is not beneficial for the control of enzymatic hydrolysis and esterification.
Example four: influence of different reaction temperatures on the reduction of various indexes
The grease of example 4-1 was prepared as follows: (1) pretreatment: heating the raw palm oil to 45 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The grease of example 4-2 was prepared as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The preparation of the fats and oils of examples 4 to 3 was as follows: (1) pretreatment: heating the raw palm oil to 65 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The preparation of the fats and oils of examples 4 to 4 was as follows: (1) pretreatment: heating the raw palm oil to 85 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The P content, acid value, and 3-MCPD ester content and GE content of the final product were determined for the process samples of examples 4-1 to 4-4, and the process parameters and performance measurements for each example are summarized in Table 5.
Table 5: results of examining Process parameters and Properties in examples 4-1 to 4-4
Figure BDA0002350868850000201
Figure BDA0002350868850000211
From the results of this example, it is clear that too high and too low reaction temperature are not favorable for the reduction of the phospholipid and 3-MCPD ester content. The preferred reaction temperature is 45-65 ℃.
Example five: influence of change of fatty acid value after lipase A reaction on reduction of indexes
The grease of example 5-1 was prepared as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 2mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The grease of example 5-2 was prepared as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The preparation of the fats and oils of examples 5 to 3 was as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 8mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The preparation of the fats and oils of examples 5 to 4 was as follows: (1) pretreatment: heating the raw palm oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 10mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined palm oil).
The P content, acid value, and 3-MCPD ester content and GE content of the final product were determined for the process samples of examples 5-1 to 5-4, and the process parameters and performance measurements for each example are summarized in Table 6.
Table 6: process parameters and Performance test results of examples 5-1 to 5-4
Figure BDA0002350868850000221
Figure BDA0002350868850000231
From the results of this example, it can be seen that when the reaction between the oil and fat and lipase a is completed, the amount of change in acid value of the oil and fat is too high or too low, which is not favorable for the subsequent esterification and control of acid value, and thus affects the reduction of the final product 3-MCPD ester. The preferable amount of increase in acid value is 3 to 8mgKOH/g, and more preferably about 5 mgKOH/g.
Example six: applicability to other oils than palm oil
The grease of example 6-1 was prepared as follows: (1) pretreatment: heating oleum Cocois to 55 deg.C, adding citric acid solution (with concentration of 50%), making citric acid content in oil reach 500ppm, stirring at constant temperature for more than 10min, adding sodium hydroxide solution (with concentration of 10%), making sodium hydroxide content in oil reach 312ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and (3) performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined coconut oil).
The grease of example 6-2 was prepared as follows: (1) pretreatment: heating the neutralized soybean oil to 55 ℃, adding a citric acid solution (with the concentration of 50%) to enable the content of citric acid in the oil to reach 500ppm, stirring at constant temperature for more than 10min, adding a sodium hydroxide solution (with the concentration of 10%) to enable the content of sodium hydroxide in the oil to reach 312ppm, and reacting for more than 5 min; adding 3% distilled water and 30ppm lipase G50 to carry out normal pressure reaction, adding 3% lipase 453 to carry out vacuum reaction when the acid value is increased by 5mgKOH/G, and carrying out conventional water washing centrifugation and drying on the grease when the acid value is reduced to 0.5mgKOH/G to obtain pretreated grease; (2) deodorizing: and (3) performing high-temperature vacuum deodorization on the pretreated grease at 260 ℃ for 1h to obtain the finished oil (refined soybean oil).
The P content, acid value, and 3-MCPD ester content and GE content of the final product were determined for the process samples of examples 6-1 and 6-2, and the process parameters and performance measurements for each example are summarized in Table 7.
Table 7: process parameters and Performance test results for examples 6-1 to 6-2
Figure BDA0002350868850000241
From the results of this example, it is clear that the present invention is also applicable to other solid and liquid oils, such as coconut oil and neutralized soybean oil.

Claims (10)

1. A method of grease treatment, characterized in that the method comprises the steps of:
(1) carrying out normal pressure reaction in a reaction system containing the grease, water and lipase A, and stopping the normal pressure reaction when the acid value of the grease is increased by 2-10 mgKOH/g; and
(2) adding lipase B into the reaction system in the step (1) to carry out vacuum reaction, and stopping the vacuum reaction when the acid value of the grease is reduced to below 1 mgKOH/g;
wherein the lipase A is a lipase from Penniclium camembertii, and the lipase B is a lipase from Candida antarctica.
2. A method of treating fats and oils according to claim 1, characterized in that it has one or more of the following features:
in the step (1), the amount of water in the reaction system is 1 to 10 wt%, preferably 3 to 5 wt% based on the weight of the oil;
in the step (1), the amount of the lipase A in the reaction system is 10-50ppm, preferably 20-40ppm based on the weight of the oil;
in the step (1), the lipase A is lipase G50;
in the step (1), stopping the normal pressure reaction until the acid value of the grease is increased by 3-8 mgKOH/g;
in the step (1), the reaction temperature is 40-80 ℃, and preferably 45-65 ℃;
in the step (2), the amount of the lipase B in the reaction system is 1-5 wt%, preferably 2-4 wt% of the weight of the oil;
in the step (2), the lipase B is selected from lipase CALB and lipase 453;
in the step (2), stopping vacuum reaction until the acid value of the grease is 0.3-1 mgKOH/g;
in the step (2), the reaction temperature is 40-80 ℃, and preferably 45-65 ℃; and
in the step (2), the vacuum degree is 10-100 mbar.
3. The method for treating fats and oils according to claim 1 or 2, further comprising an acid-base reaction step performed before the step (1), wherein the acid-base reaction step comprises: adding a citric acid solution into the grease, reacting for more than 10 minutes, and then adding an alkali liquor, and reacting for more than 5 minutes; wherein the addition amount of the citric acid is 500-2000ppm of the weight of the oil, and the amount of the alkali substance is 1-6 times of that of the citric acid.
4. The method of claim 3, wherein the method has one or more of the following features:
in the acid-base reaction, the reaction temperature is 40-80 ℃, and preferably 45-65 ℃;
the concentration of the citric acid solution is 30-80 wt%, preferably 40-60 wt%;
the addition amount of the citric acid is 500-1000 ppm;
the alkali liquor is sodium hydroxide solution or potassium hydroxide solution; the concentration of the sodium hydroxide solution or potassium hydroxide solution is preferably 5 to 20 wt%, more preferably 10 to 15 wt%;
the amount of the base is 2-4 times of the amount of the citric acid.
5. The method according to any one of claims 1 to 4, wherein the method further comprises one or more steps of water washing and drying, degumming, deacidification, alkali refining, soaping, dewaxing, decoloring and deodorizing the grease after the vacuum reaction.
6. The grease obtained by the method according to any one of claims 1 to 5; preferably, the grease has one or more of the following characteristics:
(1) the phospholipid content of the oil is less than 10ppm, preferably less than 5 ppm;
(2) the acid value of the oil is lower than 2mgKOH/g, preferably lower than 1 mgKOH/g;
(3) the content of 3-chloro-1, 2-propylene glycol ester in the grease is lower than 2mg/kg, preferably lower than 1 mg/kg; and
(4) the glycidyl ester content of the fat and oil is less than 5mg/kg, preferably less than 2 mg/kg.
7. An oil composition, wherein at least one oil in the oil composition is prepared by the method according to any one of claims 1 to 5; preferably, the fat or fat composition has one or more of the following characteristics:
(1) the phospholipid content of the oil is less than 10ppm, preferably less than 5 ppm;
(2) the acid value of the oil is lower than 2mgKOH/g, preferably lower than 1 mgKOH/g;
(3) the content of 3-chloro-1, 2-propylene glycol ester in the grease is lower than 2mg/kg, preferably lower than 1 mg/kg; and
(4) the glycidyl ester content of the fat and oil is less than 5mg/kg, preferably less than 2 mg/kg.
8. The application of lipase A and lipase B in reducing the content of oil pollutants or preparing oil with reduced content of oil pollutants; wherein the lipase A is a lipase from Penniclium camembertii, and the lipase B is a lipase from Candida antarctica.
9. The use according to claim 8, wherein the use comprises: adding water and lipase A into oil and fat, carrying out normal pressure reaction, stopping normal pressure reaction when the acid value of the oil and fat is increased by 2-10mgKOH/g, adding lipase B, carrying out vacuum reaction, and stopping vacuum reaction when the acid value of the oil and fat is reduced to below 1 mgKOH/g.
10. Use of the method of any one of claims 1-4 for reducing the phospholipid content, acid number, 3-MCPD ester content, and/or GE content of lipids.
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Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999053001A1 (en) * 1998-04-08 1999-10-21 Novo Nordisk A/S An enzymatic oil-degumming process
KR20010092006A (en) * 2001-09-05 2001-10-24 신명수 Process for preparing high purity diglyceride lipid composition
GB201019639D0 (en) * 2010-11-19 2010-12-29 Loders Croklaan Bv Method
CN102334563A (en) * 2010-07-16 2012-02-01 丰益(上海)生物技术研发中心有限公司 Method for controlling content of 3-chloro-1,2-propanediol or ester thereof in oil
CN103060088A (en) * 2011-10-18 2013-04-24 丰益(上海)生物技术研发中心有限公司 Method for controlling glycidyl ester in grease
CN103351947A (en) * 2013-06-15 2013-10-16 青岛渤海科技有限公司 Preparation method of moderately processed DHA (Docosahexaenoic acid) microalgae grease
CN103382413A (en) * 2013-07-16 2013-11-06 傅武胜 Refining process for reducing content of MCPD in tea seed oil
CN104694250A (en) * 2013-12-10 2015-06-10 丰益(上海)生物技术研发中心有限公司 Method for reducing 3-MCPD ester and/or glycidyl ester in oil
CN104705422A (en) * 2013-12-16 2015-06-17 丰益(上海)生物技术研发中心有限公司 Method for preparation of grease by enzymatic method
CN105463035A (en) * 2014-08-13 2016-04-06 丰益(上海)生物技术研发中心有限公司 Method for removing free fatty acid
CN105713936A (en) * 2014-03-14 2016-06-29 嘉必优生物技术（武汉）股份有限公司 Preparation method of microbe oil
CN105802739A (en) * 2014-12-30 2016-07-27 丰益(上海)生物技术研发中心有限公司 Deacidification method for fats and oils
WO2017012445A1 (en) * 2015-07-22 2017-01-26 北京信汇生物能源科技有限公司 Method for preparing biodiesel
CN107027903A (en) * 2017-05-16 2017-08-11 广西巴马印象生活体验产业有限公司 A kind of refinery practice of fiery sesame oil
CN108239573A (en) * 2016-12-27 2018-07-03 中粮集团有限公司 Grease and preparation method thereof
CN109957459A (en) * 2017-12-26 2019-07-02 丰益(上海)生物技术研发中心有限公司 The fatty acid for preparing the method for fatty acid and being obtained by this method

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999053001A1 (en) * 1998-04-08 1999-10-21 Novo Nordisk A/S An enzymatic oil-degumming process
KR20010092006A (en) * 2001-09-05 2001-10-24 신명수 Process for preparing high purity diglyceride lipid composition
CN102334563A (en) * 2010-07-16 2012-02-01 丰益(上海)生物技术研发中心有限公司 Method for controlling content of 3-chloro-1,2-propanediol or ester thereof in oil
GB201019639D0 (en) * 2010-11-19 2010-12-29 Loders Croklaan Bv Method
CN103060088A (en) * 2011-10-18 2013-04-24 丰益(上海)生物技术研发中心有限公司 Method for controlling glycidyl ester in grease
CN103351947A (en) * 2013-06-15 2013-10-16 青岛渤海科技有限公司 Preparation method of moderately processed DHA (Docosahexaenoic acid) microalgae grease
CN103382413A (en) * 2013-07-16 2013-11-06 傅武胜 Refining process for reducing content of MCPD in tea seed oil
CN104694250A (en) * 2013-12-10 2015-06-10 丰益(上海)生物技术研发中心有限公司 Method for reducing 3-MCPD ester and/or glycidyl ester in oil
CN104705422A (en) * 2013-12-16 2015-06-17 丰益(上海)生物技术研发中心有限公司 Method for preparation of grease by enzymatic method
CN105713936A (en) * 2014-03-14 2016-06-29 嘉必优生物技术（武汉）股份有限公司 Preparation method of microbe oil
CN105463035A (en) * 2014-08-13 2016-04-06 丰益(上海)生物技术研发中心有限公司 Method for removing free fatty acid
CN105802739A (en) * 2014-12-30 2016-07-27 丰益(上海)生物技术研发中心有限公司 Deacidification method for fats and oils
WO2017012445A1 (en) * 2015-07-22 2017-01-26 北京信汇生物能源科技有限公司 Method for preparing biodiesel
CN108239573A (en) * 2016-12-27 2018-07-03 中粮集团有限公司 Grease and preparation method thereof
CN107027903A (en) * 2017-05-16 2017-08-11 广西巴马印象生活体验产业有限公司 A kind of refinery practice of fiery sesame oil
CN109957459A (en) * 2017-12-26 2019-07-02 丰益(上海)生物技术研发中心有限公司 The fatty acid for preparing the method for fatty acid and being obtained by this method

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