CN113481248A - Method for preparing 1, 3-dioleoyl-2-palmitic acid triglyceride - Google Patents
Method for preparing 1, 3-dioleoyl-2-palmitic acid triglyceride Download PDFInfo
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Abstract
The invention discloses a method for preparing 1, 3-dioleic acid-2-palmitic acid triglyceride, which comprises the steps of controlling the reaction temperature below the melting point of saturated triglyceride, catalyzing palm stearin to carry out transesterification reaction by using lipase or an alkaline catalyst, directionally enriching saturated triglyceride, obtaining high-melting-point saturated triglyceride by using an oil-fat separation technology, replacing the palmitic acid at sn-1 and 3 positions of the saturated triglyceride by using oleic acid by using high-oleic acid vegetable oil fatty acid as an acyl donor and using sn-1 and 3-position selective lipase as a catalyst, and filtering or centrifuging to recover the lipase; and (3) separating and removing saturated fatty acid and high-melting-point triglyceride in the primary acidolysis reaction product by utilizing melting point difference, adding the recovered lipase to continue to perform secondary acidolysis reaction, and finally removing fatty acid by adopting reduced pressure distillation to obtain the structural lipid product rich in 1, 3-dioleate-2-palmitic acid triglyceride.
Description
Technical Field
The invention belongs to the technical field of grease, and particularly relates to a method for preparing 1, 3-dioleic acid-2-palmitic acid triglyceride.
Background
Infants are a group of individuals in a particular stage of growth and development with particular nutritional needs. In the aspect of infant feeding, breast milk is the best food, not only contains various necessary nutrients, but also has bile salt kinase, thereby being beneficial to the digestion and absorption of infants. Breast milk contains 3-5% of fat, is a main energy supplier for infants, and also provides various necessary functional fatty acids, fat-soluble vitamins and the like. Breast milk lipids are a complex molecular system, and the molecular composition, configuration and the like of the breast milk lipids are closely related to infant nutrition. The content of triglyceride in breast milk lipid is more than 98%, the distribution of fatty acid is unique, more than 60% of palmitic acid is in sn-2 position, and other unsaturated fatty acids such as oleic acid are mainly in sn-1 and 3 positions. Thus, the configuration of the major triglyceride in breast milk fat is 1, 3-oleic acid-sn-2 palmitic acid triglyceride (OPO), which has a significant impact on the digestion, absorption and metabolism of fat.
A large number of scholars research the influence of two isomers of OPO and POO on the digestion and absorption of lipid of infants and obtain the main conclusion that: due to the sn-1,3 position selectivity of digestive enzymes, OPO is hydrolyzed into sn-2 palmitic acid monoglyceride, and thus is directly absorbed; the palmitic acid after POO hydrolysis forms soap with calcium, magnesium and the like, and is finally discharged out of the body, and simultaneously side effects such as constipation of infants and children can be caused. Thus, OPO more readily promotes fat absorption in infants and young children. The relevant scholars also studied the effect of OPO and POO on the composition of chylomicrons lymph and found that 60% to 70% of sn-2 fatty acids remained in place, suggesting that triglyceride structure specificity affects the fatty acid profile of tissues.
The oil for infant formula milk powder is essentially a formulated product of edible oil and fat, and the attention on breast milk lipid is not enough in the early stage, so that the literature reports on the oil for formula milk powder are less. Considering the source, the oils used in infant formula are generally classified into two major categories, the first category is the blending of vegetable-based oils; the second type is the blending of milk fat and vegetable-based edible oil, and the milk fat mainly comprises cow milk fat and sheep milk fat. Microbial oil or fish oil is generally added into the compound oil to make up for the deficiency of long-chain polyunsaturated fatty acid in vegetable oil and milk fat. Therefore, in order to further simulate the lipid structure of breast milk, related enterprises have developed products similar to breast milk fat in fatty acid composition and distribution, mainly represented as OPO products.
At present, the main raw material for synthesizing OPO is palm stearin, and the related technology reports that the OPO is synthesized by using lard oil and other raw materials, but the related raw materials do not meet the national safety standard. In the production process of the palm stearin by using the palm stearin as the raw material, the palmitic acid content of the palm stearin is mainly improved by dry or wet fractionation, but the content of tripalmitin in the palm stearin is low, and only a small amount of high-saturation palm stearin can be obtained by the fractionation method, thereby causing the waste of other palm stearin components.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Accordingly, it is an object of the present invention to overcome the disadvantages of the prior art and to provide a process for preparing 1, 3-dioleoyl-2-palmitoyl triglyceride.
In order to solve the technical problems, the invention provides the following technical scheme: a process for producing 1, 3-dioleoyl-2-palmitoyl triglyceride comprising,
melting palm stearin, crystallizing saturated triglyceride to form crystal nucleus by reducing temperature, adding lipase or alkaline catalyst to catalyze palm stearin to carry out ester exchange reaction, and directionally enriching saturated triglyceride;
separating with solvent or dry method to obtain saturated triglyceride with high melting point;
carrying out acidolysis on high-melting-point saturated triglyceride by using sn-1, 3-specific lipase as a catalyst and high-oleic-acid vegetable oil fatty acid as an acyl donor, and recovering the lipase;
separating and removing saturated fatty acid and high-melting triglyceride by utilizing melting point difference, and continuously adding the recovered lipase to carry out acidolysis reaction;
and (3) removing fatty acid by reduced pressure distillation to obtain a structural lipid product rich in 1, 3-dioleate-2-palmitic acid triglyceride.
As a preferable embodiment of the method for producing 1, 3-dioleoyl-2-palmitic acid triglyceride according to the present invention, wherein: the directional enrichment of saturated triglycerides, including,
heating the temperature of the grease to 90 ℃, keeping the temperature for 30min, then reducing the temperature to 30-40 ℃ at the speed of 5-10 ℃/h, keeping the temperature for 2-4 h, forming saturated triglyceride into crystal nuclei, and then heating the temperature to 35-45 ℃ at the speed of 2-4 ℃/h.
As a preferable embodiment of the method for producing 1, 3-dioleoyl-2-palmitic acid triglyceride according to the present invention, wherein: the transesterification reaction, wherein the catalyst used is non-position selective lipase and alkaline chemical catalyst, including Novozym 435, lipase AY-30SD, sodium ethoxide and sodium methoxide.
As a preferable embodiment of the method for producing 1, 3-dioleoyl-2-palmitic acid triglyceride according to the present invention, wherein: and adding 0.5-2% of sodium ethoxide or sodium methoxide into the alkaline chemical catalyst, reacting for 8-15 hours, enriching saturated triglyceride, adding deionized water into the system to terminate the reaction, and cleaning with hot water.
As a preferable embodiment of the method for producing 1, 3-dioleoyl-2-palmitic acid triglyceride according to the present invention, wherein: and adding lipase or an alkaline catalyst to catalyze palm stearin to carry out ester exchange reaction, wherein 8-15% of Novozym 435 or lipase AY-30SD is added, and the reaction time is 24-36 h.
As a preferable embodiment of the method for producing 1, 3-dioleoyl-2-palmitic acid triglyceride according to the present invention, wherein: the method for separating and extracting saturated triglyceride comprises a wet process and a dry process, wherein the wet process comprises the steps of adding acetone and an ester exchange product into a reactant according to the proportion of 3-5 mL/g (acetone/triglyceride), fully dissolving the acetone and the ester exchange product at 60 ℃, sealing and standing at 25-35 ℃ for 10-20 hours, and separating solid fat;
the dry process is to heat the grease to 90 ℃, reduce the temperature to 35-45 ℃ at a speed of 5-10 ℃/h, keep the grease for 10-15 h, and separate and extract solid fat.
As a preferable embodiment of the method for producing 1, 3-dioleoyl-2-palmitic acid triglyceride according to the present invention, wherein: the Lipase used in the acidolysis reaction is sn-1,3 position selective Lipase, including Lipzyme RM IM, Lipzyme TL IM, Lipase DF and NS 40086; the acyl donor is a high oleic vegetable oil, including high oleic soybean oil, high oleic rapeseed oil, and high oleic peanut oil fatty acids.
As a preferable embodiment of the method for producing 1, 3-dioleoyl-2-palmitic acid triglyceride according to the present invention, wherein: the addition amount of the lipase in the primary acidolysis reaction is 6-12%, the substrate molar ratio is 1: 6-12 (triglyceride/fatty acid), the reaction temperature is 40-60 ℃, the reaction time is 8-15 hours, the stirring speed is 400-600 r/min, and after the reaction is finished, the lipase is filtered or centrifugally recovered.
As a preferable embodiment of the method for producing 1, 3-dioleoyl-2-palmitic acid triglyceride according to the present invention, wherein: the conditions for separating saturated fatty acids from the acidolysis reaction include,
heating the mixed grease to 60-70 ℃ and maintaining for 20-45 min, then reducing the temperature to 28-35 ℃ at a speed of 4-15 ℃/h, growing the crystals for 4-12 h, then reducing the temperature to 15-25 ℃ at a speed of 2-10 ℃/h, growing the crystals for 4-12 h, wherein the rotating speed is 20-40 rpm, and filtering or centrifuging to obtain the liquid oil.
As a preferable embodiment of the method for producing 1, 3-dioleoyl-2-palmitic acid triglyceride according to the present invention, wherein: the conditions of the secondary acidolysis reaction are that the lipase recovered by the primary acidolysis is added into the liquid oil, the reaction temperature is 40-55 ℃, the reaction time is 6-12 h, and the rotating speed is 300-600 r/min.
The invention has the beneficial effects that:
according to the method, lipase or an alkaline catalyst is used for catalyzing the palm stearin to carry out random ester exchange reaction, the reaction temperature is controlled to be below the melting point of tripalmitin, so that the palmitic acid is separated out from a reaction system in the form of the tripalmitin, the purpose of directionally enriching the saturated triglyceride is achieved, and the utilization rate of the palm stearin as a saturated triglyceride raw material is improved; through program cooling, the original tripalmitin is crystallized to form crystal nucleus, which is beneficial to directional enrichment of palmitic acid, and then the temperature is properly increased, so that the reaction efficiency is improved; after the acidolysis reaction, saturated fatty acid and tripalmitin in the system are separated and removed by utilizing the difference of melting points, and then secondary acidolysis reaction is continuously carried out, so that various negative shadow responses caused by high-temperature removal of fatty acid are avoided, free fatty acid is recycled, the reaction cost is reduced, and the yield of the target product in the product is increased.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
The palm stearin with the temperature of 52 ℃ is used as a raw material, the palm stearin is heated to 90 ℃ and kept for 30min, solid fat is completely melted, the original crystal structure is damaged, then the temperature is slowly reduced to 35 ℃ at the speed of 8 ℃/h and kept for 3h, saturated triglyceride is crystallized to form crystal nuclei, then the temperature is increased to 40 ℃ at the speed of 3 ℃/h, 8 percent of lipase Novozym 435 is added, the mixture reacts for 24h at the temperature, oriented transesterification is carried out, and saturated fatty acid is directionally enriched in the saturated triglyceride under the action of the melting point and is separated in a system.
After the reaction is completed, the lipase is separated by centrifugation or filtration. Adding acetone into palm stearin at a ratio of 5mL/g, dissolving at 60 deg.C, cooling to 25 deg.C, sealing, standing for 10 hr, and separating solid fat. The fatty acid composition and distribution of the resulting solid fat are shown below.
TABLE 1 fatty acid composition and distribution of palm stearin, directional transesterification product and fractionated solid fat
The method is characterized in that directional ester exchange fractionation solid fat is used as a raw material, fatty acid from high-oleic acid sunflower seed oil is used as an acyl donor, NS 40086 is used as a catalyst to perform acidolysis on palm stearin, the reaction condition is that the molar ratio of substrates is 1:8 (fractionation solid fat/fatty acid), the reaction time is 10 hours, the temperature is 50 ℃, the enzyme addition amount is 8%, and the stirring speed is 500 r/min.
After the reaction is finished, filtering or centrifugally separating lipase, heating the mixed oil to 70 ℃ and maintaining for 20min, reducing the temperature to 35 ℃ at the speed of 15 ℃/h, growing the crystals for 8h, reducing the temperature to 25 ℃ at the speed of 4 ℃/h, growing the crystals for 12h, wherein the rotating speed is 30 rpm, filtering solid fat after fractionation and crystallization is finished to obtain liquid oil, adding the filtered lipase into the reaction under the conditions of the temperature of 45 ℃, the reaction time of 8h and the stirring speed of 400 rpm, and obtaining the fatty acid composition and distribution of the product as follows:
TABLE 2 fatty acid composition and distribution of one-and two-step acidolysis products
And (3) removing fatty acid from the secondary acidolysis product through reduced pressure distillation to obtain a structural lipid product rich in 1, 3-dioleate-2-palmitic acid triglyceride.
Example 2
The palm stearin with the temperature of 44 ℃ is used as a raw material, the palm stearin is heated to 90 ℃ and is kept for 30min, solid fat is completely melted, the original crystal structure is damaged, then the temperature is slowly reduced to 30 ℃ at the speed of 5 ℃/h and is kept for 4h, saturated triglyceride forms crystal nuclei, the temperature is increased to 35 ℃ at the speed of 4 ℃/h, 2% sodium ethoxide is added, the mixture reacts for 8h at the temperature, directional random ester exchange is carried out, and saturated fatty acid is directionally enriched in the saturated triglyceride and is separated in a system under the action of a melting point.
After the reaction is finished, adding deionized water into the system to terminate the reaction, and cleaning for 3 times by using hot water at 80 ℃ to remove the catalyst. Firstly, fully dissolving palm stearin at 90 ℃, then reducing the temperature to 35 ℃ at 5 ℃/h, sealing and storing for 10h to separate solid fat. The fatty acid composition and distribution of the resulting solid fat are shown below.
TABLE 3 fatty acid composition and distribution of palm stearin, directional transesterification product and fractionated solid fat
Carrying out acidolysis on palm stearin by using directional ester exchange fractionation solid fat as a raw material, using fatty acid derived from high oleic rapeseed oil as an acyl donor and using Lipzyme RM IM as a catalyst, wherein the reaction condition is that the molar ratio of a substrate is 1:6 (fractionation solid fat/fatty acid), the reaction time is 8h, the temperature is 60 ℃, the enzyme adding amount is 10%, the stirring speed is 400 r/min, after the reaction is finished, filtering or centrifugally separating the lipase, heating the mixed oil to 60 ℃ and maintaining for 45min, reducing the temperature to 32 ℃ at the speed of 4 ℃/h, growing crystals for 4h, reducing the temperature to 20 ℃ at the speed of 10 ℃/h, growing crystals for 4h at the speed of 40 r/min, filtering the solid fat after fractionation crystallization is finished, obtaining liquid oil, adding the filtered and recovered lipase into the liquid oil for reaction, the reaction condition is 50 ℃, the reaction time is 10h, and the stirring speed is 300 r/min, the fatty acid composition and distribution of the obtained product are as follows:
TABLE 4 fatty acid composition and distribution of one-and two-step acidolysis products
And (3) removing fatty acid from the secondary acidolysis product through reduced pressure distillation to obtain a structural lipid product rich in 1, 3-dioleate-2-palmitic acid triglyceride.
Example 3
The method comprises the steps of taking 58 ℃ palm stearin as a raw material, heating the palm stearin to 90 ℃, keeping the temperature for 30min, completely melting solid fat, destroying an original crystal structure, slowly reducing the temperature to 40 ℃ at 10 ℃/h, keeping the temperature for 2h, crystallizing saturated triglyceride to form a crystal nucleus, increasing the temperature to 45 ℃ at 2 ℃/h, adding lipase AY-30SD 15% of lipase, reacting for 36h at the temperature, performing oriented random ester exchange, and directionally enriching saturated fatty acid in the saturated triglyceride through the action of a melting point and separating in a system. After the reaction is completed, the lipase is separated by centrifugation or filtration. Adding 3mL/g acetone into melting point palm stearin, dissolving at 60 deg.C, sealing at 35 deg.C, standing for 20 hr, and separating solid fat. The fatty acid composition and distribution of the resulting solid fat are shown below.
TABLE 5 fatty acid composition and distribution of palm stearin, directional transesterification product and fractionated solid fat
Carrying out acidolysis on palm stearin by using directional ester exchange fractionation solid fat as a raw material, using fatty acid from high-oleic-acid peanut oil as an acyl donor and using lipase DF as a catalyst, wherein the reaction condition is that the molar ratio of a substrate is 1:10 (fractionation solid fat/fatty acid), the reaction time is 15h, the temperature is 40 ℃, the enzyme adding amount is 12%, the stirring speed is 600 r/min, filtering or centrifugally recovering lipase, heating the mixed oil to 65 ℃ and maintaining for 30min, reducing the temperature to 30 ℃ at the speed of 8 ℃/h, growing crystals for 6h, reducing the temperature to 18 ℃ at the speed of 6 ℃/h, growing crystals for 10h at the speed of 20 r/min, after fractionation crystallization, filtering or centrifugally separating solid fat to obtain liquid oil, adding the lipase recovered by acidolysis into the liquid oil for reaction, the reaction condition is 55 ℃, the reaction time is 6h, and the stirring speed is 500 r/min, the fatty acid composition and distribution of the obtained product are as follows:
TABLE 6 fatty acid composition and distribution of one-and two-step acidolysis products
And (3) removing fatty acid from the secondary acidolysis product through reduced pressure distillation to obtain a structural lipid product rich in 1, 3-dioleate-2-palmitic acid triglyceride.
Example 4
The method comprises the steps of taking 58 ℃ palm stearin as a raw material, heating the palm stearin to 90 ℃, keeping the temperature for 30min, completely melting solid fat, destroying an original crystal structure, slowly reducing the temperature to 38 ℃ at 6 ℃/h, keeping the temperature for 3h, crystallizing saturated triglyceride to form crystal nuclei, increasing the temperature to 43 ℃ at 3 ℃/h, adding sodium methoxide with 0.5% of lipase, reacting for 15h at the temperature, performing oriented random transesterification, and directionally enriching saturated fatty acids in the saturated triglyceride under the action of a melting point and separating in a system. After the reaction is finished, adding deionized water into the system to terminate the reaction, and cleaning for 3 times by using hot water at 80 ℃ to remove the catalyst. Firstly, fully dissolving palm stearin at 90 ℃, then reducing the temperature to 45 ℃ at 10 ℃/h, and standing for 15h for separating solid fat. The fatty acid composition and distribution of the resulting solid fat are shown below.
TABLE 7 fatty acid composition and distribution of palm stearin, directional transesterification product and fractionated fixation fat
Carrying out acidolysis on palm stearin by using directional ester exchange fractionation solid fat as a raw material, using fatty acid derived from high-oleic acid sunflower seed oil as an acyl donor and using Lipzyme TL IM as a catalyst, wherein the reaction condition is that the molar ratio of a substrate is 1:12 (fractionation solid fat/fatty acid), the reaction time is 12h, the temperature is 50 ℃, the enzyme addition amount is 6%, the stirring rate is 600 r/min, filtering or centrifuging to recover the lipase, heating the mixed oil to 60 ℃ and maintaining for 30min, reducing the temperature to 28 ℃ at the speed of 10 ℃/h, growing crystals for 12h, reducing the temperature to 15 ℃ at the speed of 2 ℃/h, growing crystals for 8h at the rotation speed of 30 r/min, filtering or centrifugally separating the solid fat after fractionation crystallization to obtain liquid oil, adding the lipase recovered by acidolysis into the liquid oil for reaction, wherein the reaction condition is 40 ℃, the reaction time is 12h, the stirring rate is 600 r/min, the fatty acid composition and distribution of the obtained product are as follows:
TABLE 8 fatty acid composition and distribution of one-and two-step acidolysis products
And (3) removing fatty acid from the secondary acidolysis product through reduced pressure distillation to obtain a structural lipid product rich in 1, 3-dioleate-2-palmitic acid triglyceride.
Comparative example 1
Based on example 1, no nuclei were previously formed during the palm stearin transesterification.
The palm stearin with the temperature of 52 ℃ is used as a raw material, the palm stearin is firstly heated to 90 ℃ and kept for 30min, solid fat is completely melted, the original crystal structure is destroyed, then the temperature is slowly reduced to 40 ℃ at the speed of 8 ℃/h, Novozym 435 with 10 percent of lipase is added, the reaction is carried out for 24h at the temperature, the oriented transesterification is carried out, and the saturated fatty acid is directionally enriched in the saturated triglyceride under the action of the melting point and is separated in a system.
After the reaction is completed, the lipase is separated by centrifugation or filtration. Adding acetone into palm stearin at a ratio of 4mL/g, dissolving at 60 deg.C, cooling to 30 deg.C, sealing, standing for 15 hr, and separating to obtain solid fat. The fatty acid composition and distribution of the resulting solid fat are shown below.
TABLE 9 fatty acid composition and distribution of palm stearin, directional transesterification product and fractionated fixation fat
The traditional method adopts tripalmitin to be separated from palm stearin to prepare the human milk substitute fat, the yield is low finally because the content of the tripalmitin in the palm stearin is relatively low, but the utilization rate of the palm stearin as the tripalmitin raw material is improved through the directional enrichment reaction of random ester exchange.
By controlling the reaction temperature below the melting point of tripalmitin, saturated triglyceride can be directionally enriched in the process of transesterification of palm stearin. However, the saturated triglyceride crystals are rich and require the presence of crystal nuclei. In the grease system, when the temperature is just lower than the melting point of the tripalmitin, the grease is in a supercooled state, the tripalmitin cannot be crystallized, but when the temperature is obviously reduced to the melting point, the tripalmitin can form crystals and can be used as crystal nuclei, the palmitic acid is continuously converted on a glycerin skeleton under the action of ester exchange, and the palmitic acid formed on the tripalmitin is enriched on the crystal nuclei, so that the tripalmitin is separated from the reaction system, the reaction balance is broken, and the tripalmitin can be continuously enriched. Therefore, in this patent technique, at first through reducing the temperature, make tripalmitin form the crystal nucleus, be favorable to the enrichment of saturated triglyceride, secondly, through suitable promotion temperature, promotion reaction rate that can be better.
After the acidolysis reaction, the palmitic acid, tripalmitin and partial glyceride in the system are crystallized by utilizing the melting point difference, and finally, the separation is carried out, so that the unsaturation degree of the fatty acid in the reaction system is reduced, the acidolysis reaction can be continuously carried out again, so that the free fatty acid can be recycled, and the separation of the palmitic acid is carried out at a lower temperature, so that the sn-1,2/2 and 3 diglyceride which are byproducts formed in the primary acidolysis reaction can not be subjected to acyl transfer, and therefore, the sn-1,2/2 and 3 diglyceride can continuously act as a reaction intermediate in the secondary acidolysis reaction, so that the amount of acyl transfer in the system is reduced, and the quality of the product is improved. The palmitic acid is removed by a low-temperature split method, so that the negative influence caused by high-temperature deacidification in the continuous acidolysis reaction is avoided, and the safety of the product is improved.
Therefore, the invention utilizes the difference of melting points, catalyzes the palm stearin to carry out ester exchange reaction by lipase or chemical catalyst, and controls the reaction temperature to be below the melting point of tripalmitin to ensure that the high saturated triglyceride is directionally enriched, thereby greatly improving the utilization rate of the palm stearin; meanwhile, the technology of the invention combines acidolysis and fractionation technology, after the palmitoleic acid is used for acidolysis of the palmitoleic acid, the fractionation technology is used for removing saturated fatty acid and residual tripalmitin in a reaction system, and then repeated acidolysis reaction is carried out to obtain a structural lipid product rich in OPO, thereby avoiding adverse effects caused by high-temperature deacidification, simultaneously recycling free fatty acid, reducing production cost and improving the content of OPO in the product.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A method for preparing 1, 3-dioleoyl-2-palmitoyl triglyceride, comprising: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
melting palm stearin, crystallizing saturated triglyceride to form crystal nucleus by reducing temperature, adding lipase or alkaline catalyst to catalyze palm stearin to carry out ester exchange reaction, and directionally enriching saturated triglyceride;
separating with solvent or dry method to obtain saturated triglyceride with high melting point;
carrying out acidolysis on high-melting-point saturated triglyceride by using sn-1, 3-specific lipase as a catalyst and high-oleic-acid vegetable oil fatty acid as an acyl donor, and recovering the lipase;
separating and removing saturated fatty acid and high-melting triglyceride by utilizing melting point difference, and continuously adding the recovered lipase to carry out acidolysis reaction;
and (3) removing fatty acid by reduced pressure distillation to obtain a structural lipid product rich in 1, 3-dioleate-2-palmitic acid triglyceride.
2. The process for producing 1, 3-dioleoyl-2-palmitoyl triglyceride according to claim 1, wherein: the directional enrichment of saturated triglycerides, including,
heating the temperature of the grease to 90 ℃, keeping the temperature for 30min, then reducing the temperature to 30-40 ℃ at the speed of 5-10 ℃/h, keeping the temperature for 2-4 h, forming saturated triglyceride into crystal nuclei, and then heating the temperature to 35-45 ℃ at the speed of 2-4 ℃/h.
3. The process for producing 1, 3-dioleoyl-2-palmitoyl triglyceride as claimed in claim 1 or 2, wherein: the transesterification reaction, wherein the catalyst used is non-position selective lipase and alkaline chemical catalyst, including Novozym 435, lipase AY-30SD, sodium ethoxide and sodium methoxide.
4. The process for producing 1, 3-dioleoyl-2-palmitoyl triglyceride as claimed in claim 3, wherein: and adding 0.5-2% of sodium ethoxide or sodium methoxide into the alkaline chemical catalyst, reacting for 8-15 hours, enriching saturated triglyceride, adding deionized water into the system to terminate the reaction, and cleaning with hot water.
5. The process for producing 1, 3-dioleoyl-2-palmitoyl triglyceride according to claim 1, wherein: and adding lipase or an alkaline catalyst to catalyze palm stearin to carry out ester exchange reaction, wherein 8-15% of Novozym 435 or lipase AY-30SD is added, and the reaction time is 24-36 h.
6. The process for producing 1, 3-dioleoyl-2-palmitoyl triglyceride according to claim 1, wherein: the method for separating and extracting saturated triglyceride comprises a wet process and a dry process, wherein the wet process comprises the steps of adding acetone and an ester exchange product into a reactant according to the proportion of 3-5 mL/g (acetone/triglyceride), fully dissolving the acetone and the ester exchange product at 60 ℃, sealing and standing at 25-35 ℃ for 10-20 hours, and separating solid fat;
the dry process is to heat the grease to 90 ℃, reduce the temperature to 35-45 ℃ at a speed of 5-10 ℃/h, keep the grease for 10-15 h, and separate and extract solid fat.
7. The process for producing 1, 3-dioleoyl-2-palmitoyl triglyceride according to claim 1, wherein: the Lipase used in the acidolysis reaction is sn-1,3 position selective Lipase, including Lipzyme RM IM, Lipzyme TL IM, Lipase DF and NS 40086; the acyl donor is a high oleic vegetable oil, including high oleic soybean oil, high oleic rapeseed oil, and high oleic peanut oil fatty acids.
8. The process for producing 1, 3-dioleoyl-2-palmitoyl triglyceride according to claim 1, wherein: the addition amount of the lipase in the primary acidolysis reaction is 6-12%, the substrate molar ratio is 1: 6-12 (triglyceride/fatty acid), the reaction temperature is 40-60 ℃, the reaction time is 8-15 hours, the stirring speed is 400-600 r/min, and after the reaction is finished, the lipase is filtered or centrifugally recovered.
9. The process for producing 1, 3-dioleoyl-2-palmitoyl triglyceride according to claim 1, wherein: the conditions for separating saturated fatty acids from the acidolysis reaction include,
heating the mixed grease to 60-70 ℃ and maintaining for 20-45 min, then reducing the temperature to 28-35 ℃ at a speed of 4-15 ℃/h, growing the crystals for 4-12 h, then reducing the temperature to 15-25 ℃ at a speed of 2-10 ℃/h, growing the crystals for 4-12 h, wherein the rotating speed is 20-40 rpm, and filtering or centrifuging to obtain the liquid oil.
10. The process for producing 1, 3-dioleoyl-2-palmitoyl triglyceride according to claim 1, wherein: the conditions of the secondary acidolysis reaction are that the lipase recovered by the primary acidolysis is added into the liquid oil, the reaction temperature is 40-55 ℃, the reaction time is 6-12 h, and the rotating speed is 300-600 r/min.
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