CN114686311A - Method for pretreating raw oil and improving ester exchange rate of enzymatic ester exchange - Google Patents
Method for pretreating raw oil and improving ester exchange rate of enzymatic ester exchange Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
- A23D9/007—Other edible oils or fats, e.g. shortenings, cooking oils characterised by ingredients other than fatty acid triglycerides
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- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
- A23D9/02—Other edible oils or fats, e.g. shortenings, cooking oils characterised by the production or working-up
- A23D9/04—Working-up
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
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Abstract
The invention relates to a method for pretreating raw oil and improving the ester exchange rate of enzymatic ester exchange. The raw oil pretreatment method comprises the step of carrying out chemical ester exchange or enzymatic ester exchange on raw oil, wherein the ester exchange is stopped when the ester exchange rate is between 0.1 and 1.0 percent, and the pretreatment of the raw oil is finished. The method for improving the transesterification rate of enzymatic transesterification comprises the raw oil pretreatment step and the step of enzymatic transesterification of the pretreated raw oil obtained in the step. The invention also includes methods of extending the useful life of lipases and enzymatic transesterification methods. The method of the invention not only can obviously improve the efficiency of single-batch enzymatic transesterification reaction, but also can obviously prolong the service life of the enzyme, thereby reducing the cost of the enzyme in the transesterification process.
Description
Technical Field
The invention relates to a method for pretreating raw oil and improving the ester exchange rate of enzymatic ester exchange.
Background
The enzyme method ester exchange is a novel oil modification process, and can be used for producing special oil products such as baking, chocolate, structured fat and the like. At present, the research on the preparation of the special oil for the zero or low trans-fatty acid food at home and abroad mainly focuses on the following hydrogenation, fractionation and ester exchange technologies. The transesterification technology is an effective method for preparing the zero or low trans fatty acid food special oil, and is divided into chemical transesterification and enzymatic transesterification, compared with the enzymatic transesterification, the enzymatic transesterification has the advantages of mild reaction conditions, less byproducts, high yield and the like, and the use of strong corrosive chemicals (such as sodium methoxide) in food processing is avoided. At present, in the field of oil processing, the chemical ester exchange method is adopted at home, and although an industrialized enzyme method process is available at foreign countries, the chemical ester exchange method is not popularized and is limited by higher enzyme price, and the process optimization still has great research space.
Zhanran et al ("optimization of process for preparing plastic fat by enzymatic transesterification and research on oxidation stability"; science and technology in food industry, 2015, 8 th, 114 th-: the reaction temperature is 64 ℃, the enzyme addition amount is 7.2 percent, and the reaction time is 4.2 hours. The actual slip melting point of the enzymatic transesterification product under optimal reaction conditions can reach 37.9 ℃.
CN103037699A describes a method for processing ester-exchanged vegetable oil, which can prolong the service life of Lipozyme TL IM by processing raw oil with natural adsorbent and then performing enzymatic ester exchange.
US7452702B2 describes a method for treating raw oil by enzymatic transesterification, in which raw oil is treated by a method of single deodorization or deodorization plus purification, thereby prolonging the service life of the enzyme.
The above documents mainly optimize the process of enzymatic transesterification by controlling the respective conditions. Meanwhile, some researches focus on eliminating factors influencing enzyme activity, such as metal ions, pH value, peroxide and the like, by using the existing technical means. However, in the course of research, the inventors found that the requirements for the service life of the enzyme cannot be met by controlling the existing process conditions such as reaction temperature, reaction time and pretreatment. Thus, there remains a need in the art for techniques to extend the useful life of enzymes and reduce the cost of enzymes in transesterification processes.
Disclosure of Invention
The invention explores the process of pre-ester exchange of raw oil. The method changes the TAG composition of the raw oil by carrying out pre-transesterification treatment on the raw oil, and controls the transesterification rate of the raw oil within a certain range, thereby obviously improving the enzymatic transesterification reaction efficiency of a single batch, and simultaneously obviously prolonging the service life of enzyme, thereby reducing the cost of the enzyme in the transesterification process, and completing the invention.
In a first aspect, the present invention provides a method for pretreating a feedstock, the method comprising the step of subjecting the feedstock to chemical transesterification or enzymatic transesterification, wherein the transesterification is stopped when the transesterification rate is between 0.1 and 1.0%, thereby completing pretreatment of the feedstock.
In a second aspect, the present invention provides a method for increasing the transesterification rate of an enzymatic transesterification, the method comprising the steps of:
(1) raw oil pretreatment: performing chemical ester exchange or enzymatic ester exchange on the raw oil, wherein the ester exchange is stopped when the ester exchange rate is between 0.1 and 1.0 percent, and pretreated raw oil is obtained;
(2) and (3) enzymatic transesterification: and (2) carrying out enzymatic transesterification on the pretreated raw oil obtained in the step (1).
In a third aspect, the present invention provides a method for extending the useful life of a lipase, comprising the steps of:
(1) raw oil pretreatment: performing chemical ester exchange or enzymatic ester exchange on the raw oil, wherein the ester exchange is stopped when the ester exchange rate is between 0.1 and 1.0 percent, and pretreated raw oil is obtained;
(2) and (3) lipase treatment: performing enzymatic transesterification on the pretreated raw oil obtained in the step (1) by using lipase as a catalyst, and treating the lipase; optionally, stopping enzymatic transesterification when the transesterification rate reaches above 90%; and
(3) and (3) recovering: separating and recovering the lipase in the step (2), thereby obtaining the lipase with prolonged service life.
In a fourth aspect, the present invention provides an enzymatic transesterification method, comprising the steps of:
(1) raw oil pretreatment: performing chemical ester exchange or enzymatic ester exchange on the raw oil, wherein the ester exchange is stopped when the ester exchange rate is between 0.1 and 1.0 percent, and pretreated raw oil is obtained;
(2) and (3) lipase treatment: carrying out enzyme method transesterification on the pretreated raw oil obtained in the step (1) by using lipase as a catalyst, and treating the lipase;
(3) and (3) recovering: separating to obtain the lipase in the step (2);
(4) ester exchange: and (3) carrying out ester exchange on the pretreated raw oil obtained by the raw oil pretreatment method in the step (1) by using the lipase separated in the step (3).
In one or more embodiments of the foregoing first to fourth aspects, the raw oil is an edible oil, including natural vegetable oil, animal oil and/or microbial oil, or a fat obtained by subjecting the natural vegetable oil, animal oil or microbial oil to hydrogenation, fractionation and/or transesterification.
In one or more embodiments of the foregoing first to fourth aspects, the vegetable oil is selected from one or more of rice oil, sunflower seed oil, rape oil, palm kernel oil, peanut oil, rapeseed oil, soybean oil, cottonseed oil, safflower seed oil, perilla seed oil, tea seed oil, olive oil, cocoa bean oil, Chinese tallow tree seed oil, almond oil, tung seed oil, rubber seed oil, corn oil, wheat germ oil, sesame seed oil, castor bean seed oil, evening primrose seed oil, hazelnut oil, pumpkin seed oil, walnut oil, grape seed oil, glass endive seed oil, sea buckthorn seed oil, tomato seed oil, macadamia nut oil, coconut oil and cocoa butter; preferably, the animal oil is selected from one or more of lard, chicken oil, mutton oil, fish oil and beef tallow; preferably, the microbial oil comprises algal oil; preferably, the raw oil is used for preparing baking, chocolate or special structured fat oil.
In one or more embodiments of the foregoing first to fourth aspects, the feedstock oil comprises at least one of palmitic triglyceride vegetable oil stearin, palmitic triglyceride containing vegetable oil, or a random interesterified tallow of palmitic triglyceride containing vegetable oil; preferably, the raw oil is at least one selected from the group consisting of palm oil stearin, palm olein, palm oil fractionated stearin, randomly interesterified palm oil and randomly interesterified palm oil fractionated stearin; preferably, the raw oil contains at least palm olein and palm stearin; preferably, the weight ratio of the two is 2: 1 to 5: 1; preferably, the raw oil contains 50% or more, preferably 60% or more, more preferably 70% or more, and still more preferably 80% or more of palm olein and palm stearin by weight; preferably, the raw oil is a mixture of soybean oil, palm olein and palm stearin; preferably, the weight ratio of the three components is 1-3: 2-4: 1-3, such as 1: 3: 1.
in one or more embodiments of the foregoing first to fourth aspects, the chemical transesterification in the feedstock oil pretreatment has one or more of the following characteristics:
(1) the chemical catalyst used is an acidic catalyst or a basic catalyst, preferably selected from NaOH, KOH, NaOCH3Sodium ethoxide, organic base, solid base catalyst, sulfuric acid, sulfonic acid or solid acid catalyst, more preferably sodium methoxide, NaOH and/or KOH;
(2) the chemical catalyst is used in an amount of 0.0005-0.01 wt%, preferably 0.0005-0.005 wt%, more preferably 0.001-0.005 wt%, based on the total weight of the feedstock oil;
(3) the reaction temperature is 100-250 ℃, preferably 120-240 ℃;
(4) the reaction time is 20-90 minutes; and
(5) the vacuum degree is less than or equal to 10 mbar.
In one or more embodiments of the foregoing first to fourth aspects, the enzymatic transesterification in the feedstock oil pretreatment has one or more of the following characteristics:
(a) the Lipase used is Lipase powder or immobilized Lipase, preferably Lipase derived from Alcaligenes and/or Lipase derived from Candida, more preferably Lipozyme TL IM, Lipozyme RM or Lipase-30 SD;
(b) the addition amount of the used lipase is ten thousandth to ten thousandth of the weight of the raw oil;
(c) the reaction temperature is in the range of 40-80 ℃, preferably 70 +/-5 ℃;
(d) the reaction time is from 0.5 to 10 hours, preferably from 0.5 to 3 hours.
In one or more embodiments of the foregoing second to fourth aspects, the lipase treatment of step (2) and the transesterification of step (4) each have one or more of the following characteristics:
(i) the dosage of the lipase is 0.02-10 percent of the weight of the grease, such as 1-10 percent;
(ii) the reaction temperature is 40-80 ℃, such as preferably 70 +/-5 ℃;
(iii) the reaction time is 0.5 to 48 hours.
In a fifth aspect, the present invention provides a pretreated feedstock oil obtained by the method of the first aspect of the present invention, or a lipase obtained by the method of the third aspect of the present invention.
The sixth aspect of the present invention also provides the use of the pretreated feedstock oil obtained by the method of the first aspect of the present invention in the preparation of a lipase with an extended service life, or the use of the lipase obtained by the method of the third aspect of the present invention in enzymatic transesterification.
Detailed Description
It is to be understood that within the scope of the present invention, the above-described technical features of the present invention and the technical features described in detail below (e.g., the embodiments) may be combined with each other to constitute a preferred embodiment.
In the conventional enzymatic transesterification, the reaction is usually carried out by using refined oil as it is without pre-transesterification of the feedstock oil. The inventor finds that the enzyme activity of the method is reduced quickly in the process of enzyme recycling, and the method cannot meet the requirement. The reported raw oil treatment method is complex and has certain challenges for industrialization. The method of the invention is adopted to treat the raw oil, the raw oil is firstly subjected to certain pre-ester exchange, and the ester exchange rate is controlled within a certain range, so that the service life of the enzyme in the recycling process can be prolonged, the ester exchange rate of the single batch reaction can be improved, and the method has the advantages of simple operation and high industrialization feasibility.
In the present invention, the raw oil may be various oils and fats known in the art, especially edible oils, including vegetable oils, animal oils and microbial oils. The raw oil can be natural oil or modified oil, including oil subjected to hydrogenation, fractionation and/or ester exchange treatment. In the present invention, the vegetable oil includes, but is not limited to, one or more of rice oil, sunflower seed oil, rape oil, palm kernel oil, peanut oil, rapeseed oil, soybean oil, cottonseed oil, safflower seed oil, perilla seed oil, tea seed oil, olive oil, cocoa butter, Chinese tallow tree seed oil, almond oil, apricot kernel oil, tung seed oil, rubber seed oil, corn oil, wheat germ oil, sesame seed oil, castor bean seed oil, evening primrose seed oil, hazelnut oil, pumpkin seed oil, walnut oil, grape seed oil, glass chicory seed oil, sea buckthorn seed oil, tomato seed oil, macadamia nut oil, coconut oil, and cocoa butter. The animal oil comprises one or more of lard, chicken oil, mutton fat, fish oil and beef tallow. The microbial oil comprises algal oil. The term "oil" as used herein also includes "fats", i.e., oils that are solid at ordinary temperatures.
In some embodiments, the raw oil of the present invention is a raw oil used for producing baking, chocolate, or structured fat-specific oils.
As used herein, "pre-transesterification" or "pre-transesterification" refers to the pretreatment of a feedstock prior to the actual transesterification process. The pre-transesterification treatment may be a chemical transesterification treatment and/or an enzymatic transesterification treatment performed on the raw oil. The transesterification as described herein may be a random transesterification or a directed transesterification, but is preferably a random transesterification, i.e. preferably a chemical random transesterification or an enzymatic random transesterification.
The pre-transesterification process may be a transesterification process as is conventional in the art. For example, when the pre-exchange treatment is carried out by chemical transesterification, it can be carried out by using a chemical catalyst conventionally used for chemical transesterification. Exemplary chemical catalysts include, but are not limited to, acidic catalysts and basic catalysts. Preferably, the chemical catalyst is NaOH, KOH, NaOCH3Sodium ethoxide, organic base, solid base catalyst, sulfuric acid, sulfonic acid or solid acid catalyst; more preferably, the chemical catalyst is NaOH, KOH, NaOCH3Sulfuric acid or sulfonic acid; more preferably, the chemical catalyst is sodium methoxide, NaOH, and/or KOH.
In the pre-transesterification treatment by chemical transesterification, the amount of the chemical catalyst to be used may be 0.0005 to 0.01 wt% (i.e., 5 to 100ppm), preferably 0.0005 to 0.005 wt% (i.e., 5 to 50ppm), and particularly preferably 0.001 to 0.005 wt% (i.e., 10 to 50ppm), based on the total weight of the feedstock oil. Chemical catalysts may be used in a form well known in the art. For example, sodium methoxide is typically added as a solid to the feed oil, and NaOH and KOH are typically used as aqueous solutions, with exemplary aqueous solution concentrations ranging from 30 to 50%. The amount described herein refers to the amount of catalyst per se, not the amount of solution.
The reaction may be carried out at temperatures of 100 ℃ to 250 ℃, preferably 120 ℃ to 240 ℃.
According to the present invention, in the pre-transesterification treatment step, when the transesterification ratio reaches 0.1 to 1.0%, that is, when the transesterification ratio falls within the range, the pre-transesterification treatment is stopped. Samples can be obtained in a conventional manner during the transesterification process and the transesterification rate can be determined. The ester exchange rate was calculated as follows. Therefore, the reaction time of the preliminary ester exchange treatment is not particularly limited as long as the ester exchange rate is within the above range. An exemplary reaction time may be 20-90 minutes.
An exemplary pre-transesterification process using a chemical transesterification process includes mixing a chemical catalyst with the feedstock oil, stirring the mixture to homogeneity, and reacting the mixture at a reaction temperature as described herein. The reaction can be carried out under a vacuum degree of less than or equal to 10 mbar.
When the pre-transesterification of the present invention is carried out by enzymatic transesterification, a lipase can be used as a catalyst. As the lipase, lipase powder or immobilized lipase obtained by immobilizing lipase powder on a carrier (e.g., diatomaceous earth, ion exchange resin, etc.) can be used. The lipase to be preferably used is a lipase lacking site specificity, and includes, but is not limited to, a lipase derived from Alcaligenes, a lipase derived from Candida, and the like. Suitable lipases include various commercially available immobilized enzymes or fermentation broths thereof. Such as Lipozyme TL IM and Lopozyme RM from Novozymes (Novozymes), etc., and immobilized enzymes or fermentation broths thereof from Japan Kokuka Kogyo (AMANO Enzyme).
In the pre-transesterification by the enzymatic transesterification, the amount of the lipase to be added is usually one ten thousandth to ten thousandth of the weight of the feedstock oil. The reaction temperature for the pre-transesterification may be in the range of 40-80 deg.C, such as 70 + -5 deg.C, depending on the optimal reaction temperature for the lipase used. Similarly, when the transesterification rate reached 0.1 to 1.0%, the preliminary transesterification treatment was stopped. Depending on the specific reaction conditions, the reaction time of the enzymatic pre-transesterification treatment may be in the range of 0.5-10 hours, such as 0.5-3 hours.
An exemplary pre-transesterification treatment using an enzymatic transesterification process includes mixing a lipase with a feedstock oil, stirring the mixture to homogeneity, and reacting the mixture at a reaction temperature as described herein. The reaction can be carried out under conventional conditions.
During the pre-transesterification reaction, the reaction mass may be stirred to facilitate the reaction. The stirring rate may be 100-500 rpm.
After the chemical ester exchange reaction is finished, if necessary, the catalyst can be passivated by hot water (the water temperature is higher than the melting point of grease) or citric acid or phosphoric acid aqueous solution to stop the ester exchange reaction. Or after the enzymatic transesterification reaction is completed, if necessary, the liquid or solid lipase may be separated.
The pre-transesterification may be carried out using one raw oil, or may be carried out using a mixture of two or more raw oils. When more than two raw oils are used for pre-transesterification, the amount ratio of the raw oils is not particularly limited, and may be determined according to actual production conditions and desired products.
In some embodiments of the invention, the raw oil comprises at least one of vegetable oil stearin of palmitic triglyceride, vegetable oil containing palmitic triglyceride, or random transesterified oil and fat of vegetable oil containing palmitic triglyceride. Preferably, the vegetable-derived triglyceride is at least one selected from the group consisting of palm oil stearin, palm olein, palm oil stearin, randomly interesterified palm oil, and randomly interesterified palm oil stearin. In some embodiments, the feedstock oil comprises at least palm olein and palm stearin, preferably in a weight ratio of 2: 1 to 5: 1; preferably, the weight percentage of the palm liquid oil and the palm stearin in the raw oil is more than 50%, preferably more than 60%, more than 70% or more than 80%. In some embodiments, the raw oil may contain, in addition to palm olein and palm stearin, at least one oil selected from other vegetable oils, such as one or more of rice oil, sunflower oil, rape oil, palm kernel oil, peanut oil, rapeseed oil, soybean oil, cottonseed oil, safflower oil, perilla seed oil, tea seed oil, olive oil, cocoa butter, Chinese tallow seed oil, almond oil, tung seed oil, rubber seed oil, corn oil, wheat germ oil, sesame seed oil, castor bean seed oil, evening primrose seed oil, hazelnut oil, pumpkin seed oil, walnut oil, grape seed oil, glass chicory seed oil, sea buckthorn seed oil, tomato seed oil, macadamia nut oil, coconut oil, and cocoa butter. In some embodiments, the raw oil is soybean oil, palm olein oil and palm stearin, and the weight ratio of the soybean oil to the palm olein oil to the palm stearin is 1-3: 2-4: 1-3, such as 1: 3: 1.
after the pre-ester exchange is finished, separating grease in the reaction system. Compared with the raw oil, the oil has ester exchange rate of 0.1-1.0%. The separated grease can be used for the next enzymatic transesterification.
The invention discovers that when the grease obtained by the pre-ester exchange treatment is used for the next enzyme method ester exchange, the ester exchange rate can be obviously improved. Accordingly, the present invention provides a method for pretreating a feedstock oil, comprising the step of subjecting the feedstock oil to chemical transesterification or enzymatic transesterification (i.e., the above-mentioned preliminary transesterification treatment), wherein the transesterification rate in the chemical transesterification or enzymatic transesterification is controlled to 0.1 to 1.0%, and then the transesterification is stopped. The invention also includes a pretreated basestock oil obtained by the pretreatment method, the transesterification rate of the pretreated basestock oil is 0.1-1.0% compared to a control basestock oil which is not pretreated.
After the pre-transesterification is finished, the raw oil obtained by the pre-transesterification treatment can be subjected to enzymatic transesterification. In this enzymatic transesterification, it can be carried out using an enzyme used for conventional enzymatic transesterification, such as the lipase or immobilized enzyme thereof as described above. Typically, the enzyme is used in an amount of 0.02 to 10%, such as 1 to 10%, by weight of the fat. The reaction temperature can be 40-80 ℃, and the reaction time can be 0.5-48 hours. The reaction may be carried out with stirring. After the transesterification reaction is completed, the transesterification product and the enzyme are separated. In general, the "end of the transesterification reaction" may be determined by a predetermined reaction time or a transesterification rate of the transesterification reaction. For example, the enzymatic transesterification can be terminated when the transesterification rate is 80% or more or 90% or more.
The invention finds that the transesterification rate of the grease obtained by the pre-transesterification treatment is obviously improved when the grease is subjected to enzymatic transesterification. Accordingly, the present invention provides a method for increasing the efficiency of enzymatic transesterification, said method comprising the steps of: (1) raw oil pretreatment: performing chemical transesterification or enzymatic transesterification (i.e. the above-mentioned pre-transesterification treatment) on the raw oil, and stopping the transesterification when the transesterification rate is between 0.1 and 1.0 percent to obtain pre-treated raw oil; (2) and (3) enzymatic transesterification: and (2) carrying out enzymatic transesterification on the pretreated raw oil obtained in the step (1).
The present inventors have also found that the enzyme transesterified by the enzymatic method of the aforementioned step (2) has a significantly longer life than an enzyme transesterified by an enzymatic method which does not carry out this step. Therefore, after the enzymatic transesterification treatment step (2) of the present invention is completed, the present invention further comprises a step of separating the enzyme to obtain a lipase having an extended service life, and optionally a step of subjecting the raw oil pretreated by the raw oil pretreatment method of the present invention to enzymatic transesterification using the lipase as a catalyst.
The enzyme and the transesterification product after the end of the transesterification in step (2) can be separated by methods conventional in the art. For example, the upper oil sample is separated by sedimentation to obtain the lower enzyme.
In the enzymatic transesterification of the raw oil pretreated by the raw oil pretreatment method, which is disclosed by the invention, by taking the enzyme as a catalyst, the dosage of the enzyme is 0.02-10 percent, such as 1-10 percent of the weight of the grease. The reaction temperature can be 40-80 ℃, and the reaction time can be 0.5-48 hours. The reaction may be carried out with stirring. Preferably, the "raw oil pretreated by the raw oil pretreatment method according to the present invention" is the raw oil subjected to pre-transesterification obtained in the raw oil pretreatment step (1) described herein.
The present invention will be described below by way of specific examples. In the examples, the Triglyceride (TAG) composition of the transesterified product oil was analyzed by gas chromatography, and the transesterification rate DI (degree of interesterification) was calculated.
The transesterification ratio (DI) is used to describe the degree of transesterification. Performing TAG analysis on the samples, selecting the ratio of the peak with the most decreased content after the reaction divided by the peak with the most increased content as an indication, and calculating the DI value of each sample by using an ester exchange rate calculation formula:
wherein, Feed represents, IE (sample) represents, IE (full random) represents
The methods, starting materials, and reagents mentioned herein are those conventional in the art, unless otherwise specified.
Comparative example 1: without pre-transesterification
Preparing palm liquid oil and palm stearin (purchased from special fat and oil of Jia Li (Shanghai) Co., Ltd.) according to a ratio of 8:2(w/w) to be used as raw oil, taking 200g of the raw oil, adding 10g of immobilized enzyme Lipozyme TL IM, starting reaction at 200rpm and 70 ℃, sampling in the process, centrifugally separating immobilized enzyme particles, taking an upper oil sample for detection, analyzing triglyceride composition, and calculating ester exchange rate.
Comparative example 2: the pre-ester exchange rate is 0.04%
Pre-ester exchange: preparing palm liquid oil and palm stearin according to the proportion of 8:2(w/w) as raw oil; heating to melt the raw oil, adding 4ppm NaOH, and stirring uniformly at 200 rpm; then carrying out pre-ester exchange for 1h at 240 ℃ under the condition of 10mbar, and detecting that the ester exchange rate is 0.04% after the end;
and (3) enzymatic transesterification: taking 200g of the raw oil subjected to pre-transesterification, adding 10g of immobilized enzyme Lipozyme TL IM, starting reaction at the conditions of 200rpm and 70 ℃, sampling in the process, centrifugally separating immobilized enzyme particles, taking an upper oil sample for detection, analyzing triglyceride composition, and calculating the transesterification rate.
Comparative example 3: the pre-ester exchange rate is 1.65 percent
Pre-ester exchange: preparing palm liquid oil and palm stearin according to the proportion of 8:2(w/w) as raw oil; heating to melt the raw oil, adding 200ppm NaOH, and uniformly stirring at 200 rpm; then carrying out pre-ester exchange for 1h at 240 ℃ under the condition of 10mbar, and detecting that the ester exchange rate is 1.65% after the end;
and (3) enzymatic transesterification: taking 200g of the raw oil subjected to pre-transesterification, adding 10g of immobilized enzyme Lipozyme TL IM, starting reaction at the conditions of 200rpm and 70 ℃, sampling in the process, centrifugally separating immobilized enzyme particles, taking an upper oil sample for detection, analyzing triglyceride composition, and calculating the transesterification rate.
Example 1: pre-ester exchange is carried out by using NaOH as catalyst, and ester exchange rate is controlled to be 0.2%
Pre-ester exchange: preparing palm liquid oil and palm stearin according to the proportion of 8:2(w/w) as raw oil; heating to melt the raw oil, adding 10ppm NaOH, and uniformly stirring at 200 rpm; then carrying out pre-ester exchange for 1h at 240 ℃ under the condition of 10mbar, and detecting that the ester exchange rate is 0.2% after the end;
and (3) enzymatic transesterification: taking 200g of the raw oil subjected to pre-transesterification, adding 10g of immobilized enzyme Lipozyme TL IM, starting reaction at the conditions of 200rpm and 70 ℃, sampling in the process, centrifugally separating immobilized enzyme particles, taking an upper oil sample for detection, analyzing triglyceride composition, and calculating the transesterification rate.
Example 2: pre-ester exchange is carried out by using KOH as catalyst, and the ester exchange rate is controlled to be 0.5 percent
Pre-ester exchange: preparing palm liquid oil and palm stearin according to the proportion of 8:2(w/w) as raw oil; heating to melt the raw oil, adding 50ppm KOH, and uniformly stirring at 200 rpm; then carrying out pre-ester exchange for 1h at 240 ℃ under the condition of 10mbar, and detecting that the ester exchange rate is 0.5% after the end;
and (3) enzymatic transesterification: the enzymatic transesterification reaction was carried out in the same manner as in example 1.
Example 3: pre-ester exchange is carried out by using sodium methoxide as catalyst, and ester exchange rate is controlled to be 1%
Pre-ester exchange: preparing palm liquid oil and palm stearin according to the proportion of 8:2(w/w) as raw oil; heating to melt the raw oil, adding 20ppm sodium methoxide, and uniformly stirring at 200 rpm; then carrying out pre-ester exchange for 30min at 120 ℃ and 10mbar, and detecting that the ester exchange rate is 1% after the end;
and (3) enzymatic transesterification: the enzymatic transesterification reaction was carried out in the same manner as in example 1.
Example 4: pre-ester exchange is carried out by using immobilized enzyme TL as catalyst, and ester exchange rate is controlled to be 0.3 percent
Pre-ester exchange: preparing palm liquid oil and palm stearin according to the proportion of 8:2(w/w) as raw oil; heating to melt the raw oil, adding two parts per million (weight ratio) of immobilized enzyme TL, and uniformly stirring at 200 rpm; then carrying out pre-ester exchange for 1h at 70 ℃, and detecting that the ester exchange rate is 0.3% after the end;
and (3) enzymatic transesterification: the enzymatic transesterification reaction was carried out in the same manner as in example 1.
Example 5: the ester exchange rate is controlled to be 0.6 percent according to different raw material proportions
Pre-ester exchange: preparing palm liquid oil and palm stearin according to the proportion of 7:3(w/w) as raw oil; heating to melt the raw oil, adding 20ppm NaOH, and uniformly stirring at 200 rpm; then carrying out pre-ester exchange for 30min at 120 ℃ and 10mbar, and detecting that the ester exchange rate is 0.6% after the end;
and (3) enzymatic transesterification: the enzymatic transesterification reaction was carried out in the same manner as in example 1.
Example 6: the ester exchange rate is controlled to be less than 1 percent according to the types of different raw materials
Pre-ester exchange: preparing soybean oil, palm liquid oil and palm stearin according to the proportion of 2:6:2(w/w) as raw oil; heating to melt the raw oil, adding 10ppm NaOH, and uniformly stirring at 200 rpm; then carrying out pre-ester exchange for 30min at 120 ℃ and 10mbar, and detecting that the ester exchange rate is 0.2% after the end;
and (3) enzymatic transesterification: the enzymatic transesterification reaction was carried out in the same manner as in example 1.
Example 7: controlling the ester exchange rate to be less than 1 percent according to the types of different enzymes
Pre-ester exchange: preparing soybean oil, palm liquid oil and palm stearin according to the proportion of 2:6:2(w/w) as raw oil; heating to melt the raw oil, adding 10ppm NaOH, and uniformly stirring at 200 rpm; then carrying out pre-ester exchange for 30min at 120 ℃ and 10mbar, and detecting that the ester exchange rate is 0.2% after the end;
and (3) enzymatic transesterification: the enzymatic transesterification is carried out in the same manner as in example 1. Except that in this example the Lipozyme TL IM immobilized enzyme was replaced with Lipase-30SD (from Tianye enzyme preparations Co., Ltd.)
The transesterification products obtained by using the reaction conditions of the comparative example were used, and the transesterification ratios at different reaction times are shown in Table 1.
Table 1: change of ester interchange Rate (DI) with reaction time under different treatment conditions
| Reaction time | 2h | 4h | 6h | 8h | 10h |
| Comparative example 1 | 61.2％ | 83.1％ | 90.9％ | 91.9％ | 93.2％ |
| Comparative example 2 | 62.7％ | 84.7％ | 89.9％ | 92.4％ | 93.1％ |
| Comparative example 3 | 60.9％ | 85.2％ | 90.1％ | 90.9％ | 92.7％ |
| Example 1 | 81.6％ | 92.8％ | 97.5％ | 99.2％ | 97.6％ |
| Example 2 | 82.5％ | 93.5％ | 98.0％ | 99.3％ | 99.0％ |
| Example 3 | 81.7％ | 92.7％ | 98.2％ | 99.7％ | 99.8％ |
| Example 4 | 81.4％ | 91.6％ | 96.7％ | 98.9％ | 98.8％ |
| Example 5 | 82.4％ | 90.1％ | 95.9％ | 99.1％ | 98.7％ |
| Example 6 | 83.9％ | 91.5％ | 96.0％ | 99.0％ | 99.5％ |
| Example 7 | 88.4％ | 94.9％ | 97.1％ | 99.5％ | 99.6％ |
The data in Table 1 show that pre-transesterification of feedstock oils can increase the transesterification rate of a single batch reaction.
Comparative example of recycling experiment
Preparing palm liquid oil and palm stearin according to the proportion of 8:2(w/w) as raw oil, taking 100g of the raw oil, adding 5g of immobilized enzyme Lipozyme TL IM, starting reaction at 200rpm and 70 ℃, stopping reaction after 2 hours, settling and separating an upper oil sample for detection, analyzing triglyceride composition, and calculating ester exchange rate. The separated lower immobilized enzyme is continuously remained in the reactor, then 100g of the raw oil is added, and the enzymatic transesterification reaction of the next batch is continuously carried out.
Example of recycling experiment
100g of the raw oil pre-transesterified in example 1 was taken, 5g of immobilized enzyme Lipozyme TL IM was added, the reaction was started at 200rpm and 70 ℃ and stopped after 2 hours, the upper oil sample was separated by settling for detection, the triglyceride composition was analyzed, and the transesterification rate was calculated. The separated lower immobilized enzyme was left in the reactor, and then 100g of the raw oil pre-transesterified in example 1 was added to continue the enzymatic transesterification reaction in the next batch.
By comparing the recycling results of the above two treatment methods, the ester exchange rates of different batches of products are shown in table 2 below. The raw material used in the embodiment of the recycling experiment is the raw material oil subjected to pre-ester exchange treatment, and the data show that the service life of the enzyme can be effectively prolonged by performing the pre-ester exchange, and the ester exchange rate can still reach 67% after 20 batches of recycling experiments are performed. The raw material which is not subjected to pre-ester exchange treatment is subjected to enzyme-method ester exchange reaction, and after being recycled for 20 batches, the ester exchange rate is only 31.8 percent and is obviously lower than that of the embodiment in which pre-ester exchange is carried out.
Table 2: effect of different treatment conditions on enzyme Recycling
| Number of times of reuse | 1st | 5th | 10th | 15th | 20th |
| Comparative example of recycling experiment | 67.9％ | 57.5％ | 53.2％ | 43.6％ | 31.8％ |
| Example of recycling experiment | 74.8％ | 72.3％ | 69.8％ | 69.5％ | 67.0％ |
It can also be understood that other raw oil is subjected to the pre-transesterification treatment of the invention and then is subjected to enzymatic transesterification with the enzyme, so that the obtained enzyme also has prolonged service life, and the transesterification rate can reach more than 67% after 20 batches of recycling experiments are carried out.
Claims (10)
1. A method for pretreating raw oil, comprising the step of performing chemical transesterification or enzymatic transesterification on raw oil, characterized in that the transesterification is stopped when the transesterification rate is between 0.1 and 1.0%, thereby completing pretreatment of raw oil.
2. A method for increasing the transesterification rate of an enzymatic transesterification, the method comprising the steps of:
(1) raw oil pretreatment: performing chemical ester exchange or enzymatic ester exchange on the raw oil, wherein the ester exchange is stopped when the ester exchange rate is between 0.1 and 1.0 percent, and pretreated raw oil is obtained;
(2) and (3) enzymatic transesterification: and (2) carrying out enzymatic transesterification on the pretreated raw oil obtained in the step (1).
3. A method for extending the useful life of a lipase, comprising the steps of:
(1) raw oil pretreatment: performing chemical ester exchange or enzymatic ester exchange on the raw oil, wherein the ester exchange is stopped when the ester exchange rate is between 0.1 and 1.0 percent, and pretreated raw oil is obtained;
(2) and (3) lipase treatment: carrying out enzyme method transesterification on the pretreated raw oil obtained in the step (1) by using lipase as a catalyst, and treating the lipase; optionally, stopping enzymatic transesterification when the transesterification rate reaches above 90%; and
(3) and (3) recovering: separating and recovering the lipase in the step (2), thereby obtaining the lipase with prolonged service life.
4. An enzymatic transesterification process, characterized in that it comprises the following steps:
(1) raw oil pretreatment: performing chemical ester exchange or enzymatic ester exchange on the raw oil, wherein the ester exchange is stopped when the ester exchange rate is between 0.1 and 1.0 percent, and pretreated raw oil is obtained;
(2) and (3) lipase treatment: performing enzymatic transesterification on the pretreated raw oil obtained in the step (1) by using lipase as a catalyst, and treating the lipase;
(3) and (3) recovering: separating to obtain the lipase in the step (2);
(4) ester exchange: and (3) carrying out ester exchange on the pretreated raw oil obtained by the raw oil pretreatment method in the step (1) by using the lipase separated in the step (3).
5. The method according to any one of claims 1 to 4, wherein the raw material oil is an edible oil comprising a natural vegetable oil, an animal oil and/or a microbial oil, or a fat obtained by subjecting the natural vegetable oil, the animal oil or the microbial oil to hydrogenation, fractionation and/or transesterification;
preferably, the vegetable oil is selected from one or more of rice oil, sunflower seed oil, rape oil, palm kernel oil, peanut oil, rapeseed oil, soybean oil, cottonseed oil, safflower seed oil, perilla seed oil, tea seed oil, olive oil, cocoa bean oil, Chinese tallow seed oil, almond oil, tung seed oil, rubber seed oil, corn oil, wheat germ oil, sesame seed oil, castor bean oil, evening primrose seed oil, hazelnut oil, pumpkin seed oil, walnut oil, grape seed oil, glass chicory seed oil, sea buckthorn seed oil, tomato seed oil, macadamia nut oil, coconut oil and cocoa butter;
preferably, the animal oil is selected from one or more of lard, chicken oil, mutton oil, fish oil and beef tallow;
preferably, the microbial oil comprises algal oil;
preferably, the raw oil is used for preparing baking, chocolate or special structured fat oil.
6. The method according to claim 5, wherein the raw material oil comprises at least one of vegetable oil stearin containing palmitic triglyceride, vegetable oil containing palmitic triglyceride, or random ester-exchanged oil and fat of vegetable oil containing palmitic triglyceride;
preferably, the raw oil is at least one selected from the group consisting of palm oil stearin, palm olein, palm oil fractionated stearin, randomly interesterified palm oil and randomly interesterified palm oil fractionated stearin;
preferably, the raw oil contains at least palm olein and palm stearin; preferably, the weight ratio of the two is 2: 1 to 5: 1; preferably, the weight percentage of the palm olein and the palm stearin in the raw material oil is 50% or more, preferably 60% or more, more preferably 70% or more, and more preferably 80% or more;
preferably, the raw oil is a mixture of soybean oil, palm olein and palm stearin; preferably, the weight ratio of the three components is 1-3: 2-4: 1-3, such as 1: 3: 1.
7. the method of any one of claims 1-4,
the chemical ester exchange in the raw oil pretreatment has one or more of the following characteristics:
(1) the chemical catalyst used is an acidic catalyst or a basic catalyst, preferably selected from NaOH, KOH, NaOCH3Sodium ethoxide, organic base, solid base catalyst, sulfuric acid, sulfonic acid or solid acid catalyst, more preferably sodium methoxide, NaOH and/or KOH;
(2) the chemical catalyst is used in an amount of 0.0005-0.01 wt%, preferably 0.0005-0.005 wt%, more preferably 0.001-0.005 wt%, based on the total weight of the feedstock oil;
(3) the reaction temperature is 100-250 ℃, preferably 120-240 ℃;
(4) the reaction time is 20-90 minutes; and
(5) the vacuum degree is less than or equal to 10 mbar;
the enzymatic transesterification in the raw oil pretreatment has one or more of the following characteristics:
(a) the Lipase used is Lipase powder or immobilized Lipase, preferably Lipase derived from Alcaligenes and/or Lipase derived from Candida, more preferably Lipozyme TL IM, Lipozyme RM or Lipase-30 SD;
(b) the addition amount of the used lipase is ten thousandth to ten thousandth of the weight of the raw oil;
(c) the reaction temperature is in the range of 40-80 ℃, preferably 70 +/-5 ℃;
(d) the reaction time is from 0.5 to 10 hours, preferably from 0.5 to 3 hours.
8. The method of any one of claims 2-4, wherein the lipase treatment of step (2) and the transesterification of step (4) each have one or more of the following characteristics:
(i) the dosage of the lipase is 0.02-10 percent of the weight of the grease, such as 1-10 percent;
(ii) the reaction temperature is 40-80 ℃, such as preferably 70 +/-5 ℃;
(iii) the reaction time is 0.5 to 48 hours.
9. A pretreated feedstock oil obtained by the process of claim 1, or a lipase obtained by the process of claim 3.
10. Use of a pretreated feedstock oil obtained by the method of claim 1 for the preparation of a lipase with an extended useful life, or use of a lipase obtained by the method of claim 3 in enzymatic transesterification.
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| US20150203789A1 (en) * | 2014-01-17 | 2015-07-23 | Orochem Technologies, Inc. | Process for purification of epa (eicosapentanoic acid) ethyl ester from fish oil |
| CN105462692A (en) * | 2014-08-20 | 2016-04-06 | 丰益(上海)生物技术研发中心有限公司 | Biodiesel preparation method |
| CN111943873A (en) * | 2019-05-17 | 2020-11-17 | 北京芯友工程技术有限公司 | Semi-continuous process and device for synthesizing m-phthalic acid dihydroxy ethyl ester-5-sodium sulfonate with high ester exchange rate through catalytic reaction rectification |
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| CN103710158A (en) * | 2014-01-02 | 2014-04-09 | 华南农业大学 | Method for producing biodiesel by using kitchen wastes |
| US20150203789A1 (en) * | 2014-01-17 | 2015-07-23 | Orochem Technologies, Inc. | Process for purification of epa (eicosapentanoic acid) ethyl ester from fish oil |
| CN105462692A (en) * | 2014-08-20 | 2016-04-06 | 丰益(上海)生物技术研发中心有限公司 | Biodiesel preparation method |
| CN111943873A (en) * | 2019-05-17 | 2020-11-17 | 北京芯友工程技术有限公司 | Semi-continuous process and device for synthesizing m-phthalic acid dihydroxy ethyl ester-5-sodium sulfonate with high ester exchange rate through catalytic reaction rectification |
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