CN108642097B - Preparation method of tri-saturated fatty acid glyceride - Google Patents
Preparation method of tri-saturated fatty acid glyceride Download PDFInfo
- Publication number
- CN108642097B CN108642097B CN201810726496.9A CN201810726496A CN108642097B CN 108642097 B CN108642097 B CN 108642097B CN 201810726496 A CN201810726496 A CN 201810726496A CN 108642097 B CN108642097 B CN 108642097B
- Authority
- CN
- China
- Prior art keywords
- fatty acid
- saturated fatty
- glyceride
- lipase
- acid residues
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/6445—Glycerides
- C12P7/6454—Glycerides by esterification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention relates to the technical field of glyceride synthesis and processing, in particular to a preparation method of trisaturated fatty acid glyceride, which comprises the following steps: carrying out catalytic reaction on glyceride containing saturated fatty acid residue, saturated fatty acid and alkali under the action of lipase to obtain the trisaturated fatty acid glyceride. Wherein the saturated fatty acid corresponding to the saturated fatty acid residue is the same as the saturated fatty acid participating in the catalytic reaction, and the glyceride containing the saturated fatty acid residue has at least one ester bond or hydroxyl group which is not bonded to the saturated fatty acid residue. On the basis that the glyceride part has saturated fatty acid residues, a sufficient amount of saturated fatty acid residues are provided through corresponding saturated fatty acids, and the reaction conditions are mild, side reactions are few, and the purity of the generated trisaturated fatty acid glyceride is high by utilizing the catalytic action of lipase.
Description
Technical Field
The invention relates to the technical field of glyceride synthesis and processing, and particularly relates to a preparation method of trisaturated fatty acid glyceride.
Background
The synthesis method of the trisaturated fatty acid glyceride mainly comprises the following steps: the random transesterification of triglycerides and the reaction of glycerol with saturated fatty acids at high temperatures (180 ℃ to 200 ℃) are carried out under the action of chemical catalysts. The purity of the trisaturated fatty acid glycerides prepared by random transesterification of triglycerides with the help of chemical catalysts is not high. The glycerol and saturated fatty acid react at high temperature (180-200 ℃) and have the defects of high reaction temperature, harsh technological reaction conditions and more side reactions.
Disclosure of Invention
The purpose of the present invention is to provide a method for producing a trisaturated fatty acid glyceride, which can achieve a high purity of the trisaturated fatty acid glyceride, a high content of saturated fatty acids at the sn-2 position, simple reaction conditions, and a small number of side reactions.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a preparation method of tri-saturated fatty glyceride, which comprises the following steps: carrying out catalytic reaction on glyceride containing saturated fatty acid residue, saturated fatty acid and alkali under the action of non-directional lipase to obtain trisaturated fatty acid glyceride. Wherein the saturated fatty acid corresponding to the saturated fatty acid residue is the same as the saturated fatty acid participating in the catalytic reaction, and the glyceride containing the saturated fatty acid residue has at least one ester bond or hydroxyl group which is not bonded to the saturated fatty acid residue.
On the basis that the glyceride part has saturated fatty acid residues, a sufficient amount of saturated fatty acid residues are provided through saturated fatty acid salts generated in situ by corresponding saturated fatty acids and alkalis, and the catalytic action of non-directional lipase is utilized, so that the reaction conditions are mild, the side reactions are few, and the purity of the generated trisaturated fatty acid glyceride is high.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. Those whose specific conditions are not specified in the embodiment or examples are carried out according to the conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The method for producing a trisaturated fatty acid glyceride according to the embodiment of the present invention will be specifically described below.
Some embodiments of the present invention provide a method for preparing a tri-saturated fatty acid glyceride, comprising: carrying out catalytic reaction on glyceride containing saturated fatty acid residue, saturated fatty acid and alkali under the action of non-directional lipase to obtain trisaturated fatty acid glyceride.
Wherein the saturated fatty acid residue corresponds to the same saturated fatty acid as that participating in the catalytic reaction, e.g., a glyceride containing saturated fatty acid residues is a palmitic acid residue (other types of saturated fatty acid residues than palmitic acid residues are not excluded), and the corresponding reaction starting material saturated fatty acid is palmitic acid. And the glyceride containing a saturated fatty acid residue has at least one ester bond or hydroxyl group which is not bonded to the saturated fatty acid residue. That is, the glyceride as a raw material includes at least one of a monoglyceride, a diglyceride and a triglyceride, and a part of the ester bond thereof is an ester bond obtained by bonding a saturated fatty acid (specified above). For example, the glyceride may be a monoglyceride, a diglyceride, or a triglyceride, or a mixture of a diglyceride and a triglyceride.
It is noted that the catalytic reaction includes a transesterification reaction and an esterification reaction, and when the glyceride is mainly a triglyceride, the transesterification reaction is mainly performed, and when the glyceride includes a partial diglyceride or monoglyceride, the esterification reaction is also present.
On the basis that glyceride has partial ester bond of specific saturated fatty acid residue, a large number of fatty acid residues are provided by introducing specific saturated fatty acid, so that ester exchange and esterification reaction can be carried out under the catalysis of non-directional enzyme, the reaction condition is further reduced, side reaction is less, the purity of the generated trisaturated fatty acid glyceride is high, and the content of saturated fatty acid on sn-2 position is high.
According to some embodiments, the ratio of glycerides to saturated fatty acids is added in amounts such that the proportion of saturated fatty acid residues in the reaction system to the total fatty acid residues is greater than or equal to 90%, preferably greater than 92%, more preferably greater than 95%. For example, the saturated fatty acid may be added so that the proportion of saturated fatty acid residues in the reaction system to the total fatty acid residues is 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or the like.
According to some embodiments, the molar ratio of base to saturated fatty acid is not more than 1, preferably the molar ratio of base to fatty acid is not more than 0.025, further preferably the molar ratio of base to fatty acid is from 0.025 to 0.001.
In some embodiments, the base is NaOH, KOH, NaOC2H5、KOC2H5、NaOCH3、KOCH3Solid base catalyst and mixtures thereof, and furtherPreferably, the base is NaOH or KOH.
Through the arrangement of the proportion of the reactants, the transesterification or esterification can be fully satisfied, and then the reactants can be fully contacted, so that a reaction product with higher purity can be obtained.
According to some embodiments, the amount of non-directional Lipase added is 0.05-10%, preferably 0.1-8% of glyceride, and further preferably, the amount of Novozym 435 added is 4-8%, the amount of Lipase DF "Amano" 15 added is 0.1-1%, the amount of LipozymeTLIM added is 4-8%, and the amount of Lipase AY30G added is 0.1-1%. For example, the amount of non-directional lipase added may be 0.05%, 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%. The addition amount of the non-directional enzyme has an important influence on the reaction process, the catalytic effect cannot be achieved when the addition amount is too low, the cost is increased when the addition amount is too high, and the contact between reactants in the reaction process is influenced to a certain extent, so that the reaction effect is poor. Therefore, the catalytic action of the reaction can be sufficiently achieved by the addition amount of the non-directional lipase in the above range, so that the reaction proceeds more thoroughly within a predetermined reaction time.
In some embodiments, the Lipase comprises at least one of a non-directed Lipase, a directed Lipase, preferably the Lipase is a non-directed Lipase comprising at least one of Novozym 435, Lipase DF "Amano" 15, lipozyme tlim, and Lipase ay 30G. For example, the non-directional Lipase may be Novozym 435 or Lipase DF "Amano" 15, or a mixture of Novozym 435 and Lipase DF "Amano" 15. Preferably, the non-directional Lipase is Lipase DF "Amano" 15.
According to some embodiments, the temperature of the catalytic reaction is 30-90 ℃, preferably 35-85 ℃, further preferably, the lipozyme TLIM reaction temperature is 65-70 ℃, the Novozym 435 reaction temperature is 75-85 ℃, the reaction temperature of Lipase DF "Amano" 15 is 35-40 ℃, and the reaction temperature of Lipase AY30G is 35-40 ℃; the time of the catalytic reaction is 0.5-9 hours, and the preferable reaction time is 1-4 hours. Under this reaction temperature, reaction temperature is lower for traditional chemical catalyst's reaction temperature ratio, and its reaction goes on more easily, can keep reaction temperature invariable through the mode of water bath heating, and it is heated more evenly in the water bath heating, and heat transfer is effectual, and then makes the reaction go on more easily. Of course, other heating methods such as furnace heating may be selected to maintain the reaction temperature.
According to some embodiments, the starting saturated fatty acids involved in the reaction are selected from palmitic acid, stearic acid, caprylic acid, capric acid, lauric acid, myristic acid or arachidic acid, for example, the reactants may be glycerides and palmitates containing palmitic acid residues, glycerides and stearates containing stearic acid residues, or glycerides and laurates containing lauric acid residues. Palmitic acid or stearic acid is preferred, and palmitic acid is more preferred.
The purpose of selectively adding the alkali in the embodiment of the invention is that the alkali can generate the fatty acid salt in situ with the fatty acid in the reaction system, the fatty acid salt is strong alkali and weak acid salt, has strong ionization capacity and strong fatty acid residue activity, and the capacity of providing the fatty acid residue is far greater than that of free fatty acid or fatty acid ester, so that the speed of ester exchange reaction is accelerated, the reaction time is shortened, the using amount of lipase can be reduced, and the cost is reduced.
According to some embodiments, the glyceride containing saturated fatty acid residues may be cocoa butter, coconut oil, palm kernel oil, palm stearin, or 58-degree palm oil. Preferably, the glyceride containing saturated fatty acid residues is palm oil stearin, which is a palm oil with a high melting point (melting point 44-56 ℃) generated in the process of producing edible palm oil.
According to some embodiments, the catalytic reaction specifically comprises mixing a glyceride containing a saturated fatty acid residue, a saturated fatty acid and a base, adding the mixture to a lipase, and carrying out a stirring reaction under the condition of introducing an inert gas. The protection through inert gas can avoid the outside air to cause the influence to its reaction to the stirring can make and fully contact between the reactant, makes the reaction more abundant quick.
In some embodiments, the stirring speed during the reaction is 300 to 600r/min, preferably 400 to 500 r/min.
In some embodiments, the inert gas may be selected from nitrogen, neon, argon, etc., preferably, the inert gas is nitrogen.
According to some embodiments, the reaction system further comprises a solvent, and the reactants and the reaction product can be dissolved in the solvent by adding the solvent into the reaction system, so that phase flow between the reactants is facilitated, a good mass transfer effect is achieved in the reaction process, and the reaction effect is better. Meanwhile, after the reaction is finished, the solvent can also extract the product. The solvent may be added to the reaction system together with the reactants or may be gradually added to the reaction system during the reaction. In some embodiments, the solvent is n-hexane. In some embodiments, the solvent is added in an amount of 1 to 2 times the mass of the raw glyceride.
According to some embodiments, the catalyzed reaction is followed by removal of the soap from the organic phase by adsorption on silica gel and concentration. For example, after the catalytic reaction, the reaction mixture may be filtered and then adsorbed on silica gel to remove the soap from the organic phase.
Some embodiments of the present invention provide a method for preparing tripalmitin, comprising: and carrying out catalytic reaction on the glyceride containing palmitic acid residues, palmitic acid and alkali under the action of non-directional lipase to obtain tripalmitin. Wherein the raw material is triglyceride.
In some embodiments, trisaturated fatty acid glycerides may also be used to synthesize USU-type triglycerides, such as 1, 3-dioleate-2-palmitate triglyceride (OPO).
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Palmitic acid was weighed based on the amount of palmitic acid residues in palm stearin such that the ratio of palmitic acid residues to the total fatty acid residues in the reaction system was 90%, 1000g of palm stearin and 1000ml of n-hexane were placed in a four-necked flask, heated in a water bath until dissolved, and then mixed with palmitic acid and sodium methoxide. Wherein the molar ratio of sodium methoxide to palmitic acid is 0.02.
Then, after nitrogen is introduced, under the conditions that the water bath temperature is 35 ℃ and the rotating speed is 400r/min, 5g of non-directional Lipase DF (Amano) 15 is added after stirring to be uniform, and the reaction is carried out for 4 hours under the condition of heat preservation and stirring. Centrifuging to obtain organic phase supernatant, adsorbing with silica gel to remove soap, and performing molecular distillation to remove free fatty acid to obtain yellowish solid with tripalmitin content of 81.5% and palmitic acid content of 88.5% at sn-2 position.
Example 2
The palmitic acid was weighed based on the amount of palmitic acid residues of palm oil stearin so that the ratio of palmitic acid residues to total fatty acid residues in the reaction system was 92%, 1000g of palm oil stearin and 1200ml of n-hexane were placed in a four-necked flask, heated in a water bath until dissolved, and then mixed with palmitic acid and sodium hydroxide. Wherein the molar ratio of the sodium hydroxide to the palmitic acid is 0.01.
Then, after nitrogen is introduced, under the conditions that the water bath temperature is 40 ℃ and the rotating speed is 350r/min, 10g of non-directional lipase Lipase AY30G is added after stirring to be uniform, and the reaction is carried out for 1 hour under the condition of heat preservation and stirring. Centrifuging to obtain organic phase supernatant, adsorbing with silica gel to remove soap, and performing molecular distillation to remove free fatty acid to obtain yellowish solid with tripalmitin content of 81.3% and palmitic acid content of 90.5% at sn-2 position.
Example 3
The palmitic acid was weighed based on the amount of palmitic acid residues of palm oil stearin so that the ratio of palmitic acid residues to the total fatty acid residues in the reaction system was 94%, 1000g of palm oil stearin and 1500ml of n-hexane were placed in a four-necked flask, heated in a water bath until dissolved, and then mixed with palmitic acid and potassium hydroxide. Wherein the molar ratio of the potassium hydroxide to the palmitic acid is 0.025.
Then, after nitrogen is introduced, under the conditions that the water bath temperature is 85 ℃ and the rotating speed is 500r/min, stirring is carried out until the mixture is uniform, 50g of non-directional lipase Novozym 435 is added, and the reaction is carried out for 1 hour under the condition of heat preservation and stirring. Centrifuging to obtain organic phase supernatant, adsorbing with silica gel to remove soap, and performing molecular distillation to remove free fatty acid to obtain yellowish solid with tripalmitin content of 81.8% and palmitic acid content of 91.3% in sn-2 position.
Example 4
The palmitic acid was weighed based on the amount of palmitic acid residues of palm oil stearin so that the ratio of palmitic acid residues to the total fatty acid residues in the reaction system was 94%, 1000g of palm oil stearin and 1500ml of n-hexane were placed in a four-necked flask, heated in a water bath until dissolved, and then mixed with palmitic acid and sodium ethoxide. Wherein the molar ratio of the sodium ethoxide to the palmitic acid is 0.00125.
Then, after nitrogen is introduced, under the conditions that the water bath temperature is 65 ℃ and the rotating speed is 400r/min, stirring is carried out until the mixture is uniform, 40g of non-directional lipase lipozyme TLIM is added, and the mixture is stirred and reacted for 2 hours under the condition of heat preservation. Centrifuging to obtain organic phase supernatant, adsorbing with silica gel to remove soap, and performing molecular distillation to remove free fatty acid to obtain light yellow solid with tripalmitin content of 85.1% and palmitic acid content of 93.1% at sn-2 position.
Example 5
The palmitic acid was weighed based on the amount of palmitic acid residues of palm oil stearin so that the ratio of palmitic acid residues to total fatty acid residues in the reaction system was 96%, 1000g of palm oil stearin and 2000ml of n-hexane were placed in a four-necked flask, heated in a water bath until dissolved, and then mixed with palmitic acid and potassium hydroxide. Wherein, the potassium hydroxide and the palmitic acid are 0.016.
Then, after nitrogen is introduced, under the conditions that the water bath temperature is 40 ℃ and the rotating speed is 380r/min, stirring is carried out until the mixture is uniform, 10g of non-directional Lipase DF (Amano) 15 is added, and the mixture is stirred and reacted for 2 hours under the condition of heat preservation. Centrifuging to obtain organic phase supernatant, adsorbing with silica gel to remove soap, and performing molecular distillation to remove free fatty acid to obtain light yellow solid with tripalmitin content of 85.3% and palmitic acid content of 93.8% at sn-2 position.
Example 6
Weighing lauric acid according to the amount of lauric acid residues in palm kernel oil so that the ratio of lauric acid residues to total fatty acid residues in the reaction system is 90%, placing 1000g of palm kernel oil and 1000ml of n-hexane in a four-necked flask, heating in a water bath until dissolved, and mixing with lauric acid and potassium methoxide. Wherein the molar ratio of potassium methoxide to lauric acid is 0.02.
Then, after nitrogen is introduced, under the conditions that the water bath temperature is 85 ℃ and the rotating speed is 400r/min, 80g of non-oriented lipase Novozym 435 is added after stirring to be uniform, and the reaction is carried out for 0.5 hour under the condition of heat preservation and stirring. Centrifuging to obtain organic phase supernatant, adsorbing with silica gel to remove soap, and performing molecular distillation to remove free fatty acid to obtain light yellow solid with trilaurin content of 82.3% and lauric acid content of n-2 position of 89.5%.
Example 7
Weighing lauric acid according to the amount of lauric acid residues in palm kernel oil so that the ratio of lauric acid residues to total fatty acid residues in the reaction system is 92%, placing 1000g of palm kernel oil and 1200ml of n-hexane in a four-necked flask, heating in a water bath until dissolution, and mixing with lauric acid and potassium ethoxide. Wherein the molar ratio of the potassium ethoxide to the lauric acid is 0.0025.
Then, after nitrogen is introduced, under the conditions that the water bath temperature is 35 ℃ and the rotating speed is 300r/min, stirring is carried out until the mixture is uniform, 10g of non-directional Lipase DF (Amano) 15 is added, and the mixture is stirred and reacted for 2 hours under the condition of heat preservation. Centrifuging to obtain organic phase supernatant, adsorbing with silica gel to remove soap, and performing molecular distillation to remove free fatty acid to obtain light yellow solid with trilaurin content of 82.6% and sn-2 lauric acid content of 91.4%.
Example 8
Weighing lauric acid according to the amount of lauric acid residues in palm kernel oil so that the ratio of lauric acid residues to total fatty acid residues in the reaction system is 97%, placing 1000g of palm kernel oil and 2000ml of n-hexane in a four-necked flask, heating in a water bath until dissolved, and mixing with lauric acid and sodium hydroxide. Wherein, the molar ratio of the sodium hydroxide to the lauric acid is 0.0001.
Then, after nitrogen is introduced, under the conditions that the water bath temperature is 40 ℃ and the rotating speed is 350r/min, stirring is carried out until the mixture is uniform, 10g of non-directional Lipase DF (Amano) 15 is added, and the mixture is stirred and reacted for 5 hours under the condition of heat preservation. Centrifuging to obtain organic phase supernatant, adsorbing with silica gel to remove soap, and performing molecular distillation to remove free fatty acid to obtain yellowish solid with trilaurin content of 86.1% and lauric acid content of 95.4% at sn-2 position.
Example 9
Stearic acid was weighed so that the stearic acid residue in the reaction system was 93% based on the amount of stearic acid residues in the cocoa butter, 1000g of cocoa butter and 1500ml of n-hexane were placed in a four-necked flask, heated in a water bath until dissolved, and then mixed with stearic acid and a solid base catalyst (CAS number: 9049-93-8). Wherein the molar ratio of the solid base catalyst to the stearic acid is 0.016.
Then, after nitrogen is introduced, under the conditions that the water bath temperature is 40 ℃ and the rotating speed is 400r/min, 5g of non-directional Lipase DF (Amano) 15 is added after stirring to be uniform, and the reaction is carried out for 2 hours under the condition of heat preservation and stirring. Centrifuging to obtain organic phase supernatant, adsorbing with silica gel to remove soap, and performing molecular distillation to remove free fatty acid to obtain light yellow solid with tristearin content of 82.3% and sn-2 position stearic acid content of 91.1%.
Example 10
Stearic acid was weighed based on the amount of stearic acid residues in cocoa butter so that the proportion of stearic acid residues in the reaction system to the total fatty acid residues was 93%, 1000g of cocoa butter and 1500ml of n-hexane were put into a four-necked flask, heated in a water bath until dissolved, and then mixed with stearic acid and potassium hydroxide. Wherein the molar ratio of the potassium hydroxide to the stearic acid is 0.001.
Then, after nitrogen is introduced, under the conditions that the water bath temperature is 75 ℃ and the rotating speed is 440r/min, 60g of non-directional lipase Novozym 435 is added after stirring to be uniform, and the reaction is carried out for 1 hour under the condition of heat preservation and stirring. Centrifuging to obtain organic phase supernatant, adsorbing with silica gel to remove soap in the organic phase, and performing molecular distillation to remove free fatty acid to obtain light yellow solid with tristearin content of 87.1% and stearic acid content in sn-2 position of 92.3%.
Example 11
The palmitic acid was weighed based on the amount of palmitic acid residues of palm oil stearin so that the ratio of palmitic acid residues to the total fatty acid residues in the reaction system was 85%, 1000g of palm oil stearin and 2000ml of n-hexane were placed in a four-necked flask, heated in a water bath until melted, and then mixed with palmitic acid and sodium hydroxide. Wherein the molar ratio of the sodium hydroxide to the palmitic acid is 0.016.
Then, after nitrogen is introduced, under the conditions that the water bath temperature is 40 ℃ and the rotating speed is 380r/min, stirring is carried out until the mixture is uniform, 10g of non-directional Lipase DF (Amano) 15 is added, and the mixture is stirred and reacted for 2 hours under the condition of heat preservation. Centrifuging to obtain organic phase supernatant, adsorbing with silica gel to remove soap, and performing molecular distillation to remove free fatty acid to obtain yellowish solid with tripalmitin content of 64.6% and palmitic acid content of 80.4% at sn-2 position.
Example 12
The palmitic acid was weighed based on the amount of palmitic acid residues of palm oil stearin so that the proportion of palmitic acid residues in the reaction system to the total fatty acid residues was 94%, 1000g of palm oil stearin was placed in a four-necked flask, heated in a water bath until dissolved, and then mixed with palmitic acid and sodium hydroxide. Wherein the molar ratio of the sodium hydroxide to the palmitic acid is 0.025.
Then, after nitrogen is introduced, under the conditions that the water bath temperature is 85 ℃ and the rotating speed is 500r/min, stirring is carried out until the mixture is uniform, 50g of non-directional lipase Novozym 435 is added, and the reaction is carried out for 1 hour under the condition of heat preservation and stirring. Extracting with 1500ml n-hexane, centrifuging to obtain organic phase supernatant, adsorbing with silica gel to remove soap, and performing molecular distillation to remove free fatty acid to obtain light yellow solid with tripalmitin content of 43.3% and sn-2 upper palmitic acid content of 88.2%.
Example 13
The palmitic acid was weighed based on the amount of palmitic acid residues of palm oil so that the ratio of palmitic acid residues to total fatty acid residues in the reaction system was 96%, 1000g of palm stearin and 2000ml of n-hexane were placed in a four-necked flask, heated in a water bath until dissolved, and then mixed with palmitic acid and potassium hydroxide. Wherein the molar ratio of the potassium hydroxide to the palmitic acid is 0.016. After nitrogen is introduced, 60g of immobilized 1, 3-bit specific lipase RMIM is added after stirring to be uniform under the conditions that the water bath temperature is 65 ℃ and the rotating speed is 380r/min, and the mixture is stirred and reacted for 2 hours under the heat preservation condition. Centrifuging to obtain organic phase supernatant, adsorbing with silica gel to remove soap in the organic phase, and performing molecular distillation to remove free fatty acid to obtain light yellow solid with palmitic acid content of 76.6% at sn-2 position.
Wherein, the iodine value of the palm oil subjected to the reaction is 35, and the iodine value of the glyceride product obtained after the reaction is 20.3.
Example 14
This example differs from example 5 only in that 0.5g of the non-directional Lipase DF "Amano" 15 was added. The content of tripalmitin in the product obtained by the reaction is 75.8%, and the content of palmitic acid on the sn-2 position is 85.9%.
Example 15
This example differs from example 5 only in that 100g of the non-directional Lipase DF "Amano" 15 was added. The content of tripalmitin in the product obtained by the reaction is 80.6%, and the content of palmitic acid on the sn-2 position is 86.8%.
Example 16
This example differs from example 5 only in that the temperature of the water bath for the catalytic reaction was 30 ℃. The content of tripalmitin in the product obtained by the reaction is 65.8%, and the content of palmitic acid on the sn-2 position is 80.6%.
Example 17
This example differs from example 5 only in that the temperature of the water bath for the catalytic reaction was 90 ℃. The content of tripalmitin in the product obtained by the reaction is 64.2%, and the content of palmitic acid on the sn-2 position is 79.3%.
Comparative example 1
30kg of palm oil stearin was weighed into a 100L pilot reactor, 5kg of sodium palmitate was added, nitrogen gas was introduced, and the mixture was heated with stirring. Then, the reaction temperature is stabilized at 180 ℃, the rotating speed is 300r/min, and the reaction lasts for 12 hours. Cooling to 50 deg.C, adding n-hexane to dissolve solid, centrifuging to obtain organic phase supernatant, adsorbing with silica gel to remove soap, and concentrating to obtain light yellow solid with tripalmitin content of 40.7% and palmitic acid content of 63.6% at sn-2 position. .
Comparative example 2
30kg of palm oil stearin was weighed into a 100L pilot reactor, 5kg of sodium palmitate was added, nitrogen gas was introduced, and the mixture was heated with stirring. Then, the reaction temperature is stabilized at 185 ℃, the rotating speed is 400r/min, and the reaction is carried out for 20 hours. Cooling to 50 deg.C, adding n-hexane to dissolve solid, and adding water to adsorb soap. Filtering, adsorbing with silica gel to remove soap from organic phase, and concentrating to obtain yellowish solid with tripalmitin content of 41.2% and palmitic acid content of 64.2% at sn-2 position.
Comparative example 3
The palmitic acid was weighed based on the amount of palmitic acid residues of the palm oil so that the ratio of the palmitic acid residues to the total fatty acid residues in the reaction system was 96%, 1000g of palm stearin and 1500ml of n-hexane were placed in a four-necked flask, heated in a water bath until dissolved, and then mixed with the palmitic acid. After nitrogen is introduced, under the conditions that the temperature of the water bath is 40 ℃ and the rotating speed is 380r/min, stirring is carried out until the mixture is uniform, 10g of non-directional Lipase DF Amano 15 is added, and the mixture is stirred and reacted for 2 hours under the condition of heat preservation. Centrifuging to obtain organic phase supernatant, adsorbing with silica gel to remove soap, and concentrating to obtain light yellow solid with tripalmitin content of 51.2% and palmitic acid content of 78% at sn-2 position.
Through the examples 1 to 10, it can be seen that the trisaturated fatty acid glyceride prepared by the embodiment of the invention has the purity of more than 80%, the reaction condition is mild, and the side reaction is less. As is clear from comparison between comparative example 5 and example 11, the amount of saturated fatty acid added has a large influence on the purity of the obtained trisaturated fatty acid glyceride, and when the amount is added so that the proportion of saturated fatty acid residues in the reaction system to the total fatty acid residues is 90%, a product having a high purity can be obtained. As can be seen from comparison of example 3 and example 12, the addition of a solvent to the reaction system is advantageous in terms of the effect of catalyzing the reaction and the purity of the product. Comparing example 5 with example 13, it can be seen that the non-directional lipase has a very good catalytic effect with respect to the directional lipase in the preparation method according to the embodiment of the present invention. It can be seen by comparing example 5 with examples 14 and 15 that the higher the amount of lipase added, the higher the content of trisaturated fatty acid glycerides. By comparing example 5 with examples 16 and 17, it can be seen that the catalytic reaction effect is significantly deteriorated when the temperature is too high and too low. By comparing examples 1-10 with comparative examples 1-3, it can be seen that the method of the embodiment of the present invention has mild reaction conditions, reduced side reactions and greatly improved purity compared to the method of producing trisaturated fatty acid glycerides only under the action of the lipase or the chemical catalysis of the fatty acid salts.
In conclusion, on the basis that the glyceride part has saturated fatty acid residues, a sufficient number of saturated fatty acid residues are provided through saturated fatty acid salts generated in situ by corresponding saturated fatty acids and alkalis, and the reaction conditions are mild, side reactions are few, and the purity of the generated trisaturated fatty acid glyceride is high by utilizing the catalytic action of the non-directional lipase.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (12)
1. A preparation method of tri-saturated fatty glyceride is characterized by comprising the following steps:
carrying out catalytic reaction on glyceride containing saturated fatty acid residue, saturated fatty acid and alkali under the action of lipase to obtain the trisaturated fatty acid glyceride;
wherein saturated fatty acids corresponding to the saturated fatty acid residues are the same as the saturated fatty acids participating in the catalytic reaction, and the glyceride containing the saturated fatty acid residues has at least one ester bond or hydroxyl group which is not bonded to the saturated fatty acid residues, and the proportion of the saturated fatty acid residues in the reaction system of the glyceride and the saturated fatty acids is greater than or equal to 90% of the total fatty acid residues;
the molar ratio of the base to the saturated fatty acid is not more than 1;
the Lipase is a non-directional Lipase, and the non-directional Lipase comprises at least one of Novozym 435, Lipase DF "Amano" 15, LipozymeTLIM and Lipase AY 30G;
the glyceride containing saturated fatty acid residue is palm oil stearin containing palmitic acid residue, palm kernel oil containing lauric acid residue or cocoa butter containing stearic acid residue, and the saturated fatty acid corresponding to the saturated fatty acid residue is palmitic acid, lauric acid or stearic acid.
2. The method for producing triglycerides of saturated fatty acids according to claim 1, wherein the ratio of saturated fatty acid residues in the reaction system of the glycerides with the saturated fatty acids is more than 92% of the total fatty acid residues.
3. The method for producing triglycerides of saturated fatty acids according to claim 1, wherein the ratio of saturated fatty acid residues in the reaction system of the glycerides with the saturated fatty acids is more than 95% of the total fatty acid residues.
4. The method for producing trisaturated fatty acid glycerides according to claim 1, wherein the lipase is added in an amount of 0.05 to 10% based on the glycerides.
5. The method for producing trisaturated fatty acid glycerides according to claim 1, wherein the lipase is added in an amount of 0.1 to 8% based on the glycerides.
6. The method for producing trisaturated fatty acid glycerides according to claim 1, wherein the temperature of the catalytic reaction is 30 to 90 ℃ and the time of the catalytic reaction is 0.5 to 9 hours.
7. The method for producing trisaturated fatty acid glycerides according to claim 1, wherein the temperature of the catalytic reaction is 35 to 85 ℃ and the time of the catalytic reaction is 1 to 4 hours.
8. The method for producing glycerol trisaturated fatty acids as described in claim 1, wherein said glycerol ester comprises at least one of a monoglyceride and a diglyceride.
9. The method for producing trisaturated fatty acid glycerides according to claim 1, wherein the base is NaOH, KOH, NaOC2H5、KOC2H5、NaOCH3、KOCH3Solid base catalysts and mixtures thereof.
10. The method for producing trisaturated fatty acid glycerides according to claim 1, wherein the base is NaOH or KOH.
11. The method according to claim 1, wherein the catalytic reaction comprises mixing the glyceride containing saturated fatty acid residues with the saturated fatty acids and the base, adding the lipase, and stirring under an inert gas atmosphere.
12. The method for preparing trisaturated fatty acid glyceride according to claim 1, wherein said reaction system further comprises a solvent, and said solvent is n-hexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810726496.9A CN108642097B (en) | 2018-07-04 | 2018-07-04 | Preparation method of tri-saturated fatty acid glyceride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810726496.9A CN108642097B (en) | 2018-07-04 | 2018-07-04 | Preparation method of tri-saturated fatty acid glyceride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108642097A CN108642097A (en) | 2018-10-12 |
| CN108642097B true CN108642097B (en) | 2021-07-09 |
Family
ID=63750993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810726496.9A Active CN108642097B (en) | 2018-07-04 | 2018-07-04 | Preparation method of tri-saturated fatty acid glyceride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108642097B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108796000A (en) * | 2018-07-04 | 2018-11-13 | 嘉必优生物技术（武汉）股份有限公司 | Three saturated fatty acid glycerides of one kind and USU type triglycerides |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080241897A1 (en) * | 2005-09-12 | 2008-10-02 | Novozymes A/S | Enzymatic Oil Interesterification |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130136013A (en) * | 2005-04-27 | 2013-12-11 | 엔지모테크 리미티드 | Human milk fat substitutes |
| DK2115107T3 (en) * | 2007-02-28 | 2018-06-18 | Loders Croklaan Bv | PROCEDURE FOR PREPARING A GLYCERIDE COMPOSITION |
| CN104705422B (en) * | 2013-12-16 | 2020-10-30 | 丰益(上海)生物技术研发中心有限公司 | Method for preparing grease by enzyme method |
| CN106591386A (en) * | 2014-07-07 | 2017-04-26 | 嘉必优生物技术（武汉）股份有限公司 | Preparation method of composition containing 2-tripalmitin |
| CN105341164A (en) * | 2014-08-22 | 2016-02-24 | 中粮营养健康研究院有限公司 | Preparation method of human milk fat substitute, human milk fat substitute prepared by method, and use of milk fat substitute |
-
2018
- 2018-07-04 CN CN201810726496.9A patent/CN108642097B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080241897A1 (en) * | 2005-09-12 | 2008-10-02 | Novozymes A/S | Enzymatic Oil Interesterification |
Non-Patent Citations (2)
| Title |
|---|
| Enzymatic hydrolysis of palm stearin to produce diacylglycerol with a highly thermostable lipase;Yang Xu;《Eur. J. Lipid Sci. Technol.》;20131231;第115卷;第564–570页 * |
| Physical properties of lipase-catalyzed interesterification of palm stearin with canola oil blends;Wai Lin Siew;《Eur. J. Lipid Sci. Technol》;20071231;第109卷;第97–106页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108642097A (en) | 2018-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU551956B2 (en) | Fat processing | |
| JP3720194B2 (en) | Method for producing partial glycerides | |
| AU2019299299B2 (en) | Method for lowering iodine value of glyceride | |
| EP0126416B1 (en) | Reaction method for transesterifying fats and oils | |
| Castillo et al. | The role of silica gel in lipase‐catalyzed esterification reactions of high‐polar substrates | |
| US4263216A (en) | Diglyceride manufacture | |
| JPS6250115B2 (en) | ||
| EP0257388A2 (en) | Process for transesterifying fats | |
| JPH0439995B2 (en) | ||
| CN108823255B (en) | Preparation method of tri-saturated fatty acid glyceride | |
| Bradoo et al. | High yields of ascorbyl palmitate by thermostable lipase-mediated esterification | |
| JP2005287510A (en) | Method for enzymatically synthesizing triglyceride of unsaturated fatty acid | |
| CN108795998B (en) | Method for reducing iodine value of glyceride | |
| CN108642097B (en) | Preparation method of tri-saturated fatty acid glyceride | |
| CN108795999B (en) | Preparation method of tri-saturated fatty acid glyceride | |
| WO2020007334A1 (en) | Tri-saturated fatty acid glyceride and usu-type triglyceride | |
| JPH08294394A (en) | Production of diglyceride | |
| US3878231A (en) | Acylation of symmetrical diglycerides with fatty acid anhydride | |
| CN111187800A (en) | Method for efficiently synthesizing phytosterol ester by enzyme method | |
| US2442534A (en) | Mono-and/or diglyceride preparation | |
| NZ772540B2 (en) | Method for lowering iodine value of glyceride | |
| JP2711391B2 (en) | Method for producing reformed oil | |
| JP4945838B2 (en) | Oil and fat manufacturing method | |
| JPH0971594A (en) | Production of fatty acid ester of sugar or sugaralcohol | |
| JPH012588A (en) | Modified oil manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |