CN109082447B - Preparation method of mixed ester rich in OPO structure ester - Google Patents
Preparation method of mixed ester rich in OPO structure ester Download PDFInfo
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Abstract
The invention provides a preparation method of a mixed ester rich in OPO structure fat, which belongs to the technical field of organic synthesis. The data of the examples show that the OPO content (calculated by C52 triglyceride content in national standard), the content of palmitic acid at the 2-position in all palmitic acid and the content of the remaining palmitic acid triglyceride in the mixed ester rich in OPO structural fat prepared by using fatty acid ethyl ester/fatty acid and palm stearin are respectively 46.35%/44.17%, 60.73%/57.60% and 5.67%/4.07%, and the product indexes meet the requirements of national standard GB 30604-.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of mixed ester rich in OPO structure ester.
Background
Human milk is the best food source for infants, and provides the infants with comprehensive and balanced nutrition to promote the growth and development of the infants. The human milk contains about 4% of lipid, wherein the proportion of triglyceride is more than 98%, and the triglyceride is one of main nutrient components in the human milk and provides certain energy for infants. Due to the lack of breast feeding conditions in some regions, infants who cannot receive breast feeding mainly use formula milk powder as a substitute. However, the structure of fatty acid in the traditional formula milk powder is greatly different from that of breast milk fat, so that the traditional formula milk powder is not beneficial to the healthy growth of infants. Therefore, it is of utmost importance to select a suitable infant formula. The 1, 3-dioleoyl-2-palmitic acid triglyceride (OPO structure fat) is used as a novel breast milk fat substitute, and the OPO structure fat is added into the formula milk powder to achieve the feeding effect which is most similar to breast milk.
The synthesis of OPO structure lipid is realized by rearranging the position of fatty acid on glycerol molecule through enzymatic transesterification, and the fatty acid composition and structure of the OPO structure lipid are more similar to breast milk fat. Compared with the traditional formula milk powder, the OPO type formula milk powder has the advantages that the palmitic acid is mainly concentrated on the Sn-2 position (the content of the palmitic acid at the 2 position is higher than 40%), the absorption of fatty acid by a human body can be promoted, the proper energy supply is ensured, the possibility of calcium soap generation is effectively reduced, the defecation difficulty of infants is reduced, the absorption and utilization of energy and mineral substances of the infants can be improved, the loss of calcium, magnesium ions and other nutrient components in the body is reduced, and the physical constitution and the natural growth of bones of the infants are promoted. Therefore, the OPO structural fat added into the milk powder can achieve the feeding effect similar to that of breast milk.
At present, tea oil and olive oil are adopted to provide oleic acid to synthesize OPO structural grease, but the cost is high, and the grease raw material source is few; the commercial oleic acid takes mixed oil as a raw material, the source of the commercial oleic acid cannot be traced, and the fatty acid prepared by medium-pressure hydrolysis of the oil needs to be rectified and purified at high temperature, so that the production process is increased.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a mixed ester rich in OPO structure ester, which takes high-oleic-acid peanut oil as a raw material, reduces the steps of oleic acid purification, shortens the flow, improves the product safety and can reach the national standard.
The invention provides a preparation method of a mixed ester rich in OPO structure lipid, which comprises the following steps:
1) carrying out alcoholysis reaction or medium-pressure hydrolysis reaction on the high-oleic-acid peanut oil to obtain a reaction product; the oleic acid content of the high-oleic-acid peanut oil is more than or equal to 70 percent; the reaction product of the alcoholysis reaction is fatty acid ethyl ester, and the reaction product of the medium-pressure hydrolysis reaction is fatty acid;
2) mixing the reaction product obtained in the step 1), palm stearin and Sn-1, 3-bit specific lipase, and then carrying out ester exchange reaction to obtain the mixed ester rich in OPO structural fat.
Preferably, the temperature of alcoholysis in the step 1) is 60-80 ℃, and the time of alcoholysis is 1-3 h.
Preferably, the temperature of medium-pressure hydrolysis in the step 1) is 240-260 ℃, and the time of medium-pressure hydrolysis is 8-10 h.
Preferably, the pressure of the medium-pressure hydrolysis in the step 1) is 24-28 kg/cm2。
Preferably, the temperature of the ester exchange reaction in the step 2) is 50-90 ℃, and the time of the ester exchange reaction is 1-6 h.
Preferably, the molar ratio of the reaction product to the palm stearin in the step 2) is 2: 1-6: 1.
preferably, the Sn-1, 3-position obligate lipase in the step 2) is Novoxin immobilized lipase 40086, Novoxin immobilized lipase T L IM, immobilized Candida sp.99-125 lipase or immobilized porcine pancreatic lipase.
Preferably, the mass of the Sn-1, 3-position specific lipase in the step 2) is 2-10% of the total mass of the reaction product and the palm stearin.
The beneficial technical effects are as follows: the preparation method provided by the invention takes high oleic peanut oil as a raw material, and a reaction product obtained through alcoholysis reaction or medium pressure hydrolysis reaction can be directly synthesized with palm stearin under the catalytic action of Sn-1, 3-position specific lipase to obtain the mixed ester rich in the OPO structure fat, so that the purification step of oleic acid is omitted, the process flow is shortened, and the safety of the product is improved. The data of the examples show that the OPO content (calculated by C52 triglyceride content in national standard), the content of palmitic acid at the 2-position in all palmitic acid and the content of the remaining palmitic acid triglyceride in the mixed ester rich in OPO structural fat prepared by using fatty acid ethyl ester/fatty acid and palm stearin are respectively 46.35%/44.17%, 60.73%/57.60% and 5.67%/4.07%, and the product indexes meet the requirements of national standard GB 30604-.
Description of the drawings:
FIG. 1 is a flow chart of a process for producing 1, 3-dioleoyl-2-palmitoyl triglyceride in accordance with the present invention;
FIG. 2 is a gas chromatogram of the fatty acid composition of the fatty acid ethyl ester obtained in example 1;
FIG. 3 is the effect of the molar ratio of fatty acid ethyl esters and palm stearin on the synthesis in example 1;
FIG. 4 is a graph showing the effect of the transesterification reaction time on the synthesis in example 2;
FIG. 5 is a graph showing the effect of enzyme content on the synthesis in example 3;
FIG. 6 is a graph showing the effect of the transesterification reaction temperature on the synthesis in example 4;
FIG. 7 is a thin layer analysis chart of the objective product obtained in example 5;
FIG. 8 is a gas chromatogram of the objective product obtained in example 5;
FIG. 9 is a gas chromatogram of the triglyceride composition of the objective product obtained in example 5;
FIG. 10 is a gas chromatogram of the fatty acid composition of the triglyceride in the objective product obtained in example 5;
FIG. 11 is a gas chromatogram of the Sn-2 fatty acid composition in triglycerides of the target product obtained in example 5;
FIG. 12 is a graph of the SFC versus temperature for the target product obtained in example 5;
FIG. 13 is a gas chromatogram of the triglyceride composition of the objective product obtained in example 6;
FIG. 14 is a gas chromatogram of the fatty acid composition of the triglyceride whole sample in the objective product obtained in example 6;
FIG. 15 is a gas chromatogram showing the composition of Sn-2 fatty acids in triglycerides of the objective products obtained in example 6.
Detailed Description
The invention provides a preparation method of a mixed ester rich in OPO structure lipid, which comprises the following steps:
1) carrying out alcoholysis reaction or medium-pressure hydrolysis reaction on the high-oleic-acid peanut oil to obtain a reaction product; the oleic acid content of the high-oleic-acid peanut oil is more than or equal to 70 percent; the reaction product of the alcoholysis reaction is fatty acid ethyl ester, and the reaction product of the medium-pressure hydrolysis reaction is fatty acid;
2) mixing the reaction product obtained in the step 1), palm stearin and Sn-1, 3-bit specific lipase, and then carrying out ester exchange reaction to obtain the mixed ester rich in OPO structural fat.
Carrying out alcoholysis reaction or medium-pressure hydrolysis reaction on the high-oleic-acid peanut oil to obtain a reaction product; the oleic acid content of the high-oleic-acid peanut oil is more than or equal to 70 percent; the reaction product of the alcoholysis reaction is fatty acid ethyl ester, and the reaction product of the medium-pressure hydrolysis reaction is fatty acid.
In the invention, the alcoholysis temperature is preferably 60-80 ℃, and more preferably 65-75 ℃; the alcoholysis time is preferably 1-3 h, and more preferably 1.5-2.5 h.
In the present invention, the alcoholysis is preferably carried out under stirring conditions. In the present invention, the stirring method is not particularly limited, and a stirring method known to those skilled in the art may be used.
In the invention, the alcoholysis is preferably carried out after the high-oleic-acid peanut oil, the ethanol and the sodium hydroxide are mixed to obtain the fatty acid ethyl ester.
In the invention, the mass ratio of the high oleic peanut oil, the ethanol and the sodium hydroxide is preferably 200: 60-100: 1, more preferably 200: 75-85: 1.
the invention also preferably comprises the steps of carrying out reduced pressure distillation, layering, washing and dehydration on the alcoholysis reaction solution in sequence to obtain the fatty acid ethyl ester.
In the invention, the temperature of the reduced pressure distillation is preferably 40-60 ℃, and more preferably 45-55 ℃; the time of the reduced pressure distillation is preferably 0-60 min, more preferably 40-50 min, and the pressure of the reduced pressure distillation is preferably 0.03-0.05 kg/cm2More preferably 0.035 to 0.045kg/cm2. The invention is steamed by reduced pressure distillationExcess ethanol was removed.
In the present invention, the separation is preferably performed by placing the distilled liquid in a separating funnel and standing for separation to obtain an upper layer liquid. The invention separates the sodium hydroxide, the glycerin and the soap at the lower layer by standing and layering.
In the present invention, the water washing is preferably performed on the upper layer liquid.
In the present invention, the washing with water is preferably performed with distilled water at 50 ℃. The number of times of washing with water is not particularly limited, and the washing is carried out until the washing is neutral.
In the present invention, the dehydration is preferably performed by rotary evaporation under reduced pressure of the upper layer liquid after washing.
In the invention, the temperature of the reduced pressure rotary evaporation is preferably 70-90 ℃, and more preferably 75-85 ℃; the time of the reduced pressure rotary evaporation is preferably 80-100 min, more preferably 85-95 min, and the pressure of the reduced pressure rotary evaporation is preferably 0.03-0.05 kg/cm2More preferably 0.035 to 0.045kg/cm2。
In the invention, the medium-pressure hydrolysis temperature is preferably 240-260 ℃, and more preferably 240-255 ℃; the medium-pressure hydrolysis time is preferably 8-10 h; more preferably 8-9 h; the pressure intensity of the medium-pressure hydrolysis is preferably 24-28 kg/cm2More preferably 24 to 27kg/cm2。
In the invention, the medium-pressure hydrolysis is preferably carried out after the high-oleic-acid peanut oil is mixed with water, so as to obtain the fatty acid.
In the invention, the volume ratio of the high oleic peanut oil to water is preferably 1: 1.
in the invention, the medium-pressure hydrolysis temperature is preferably 240-255 ℃; the pressure intensity of the medium-pressure hydrolysis is preferably 24-27 kg/cm2The medium-pressure hydrolysis time is preferably 8-9 h.
The content of oleic acid in the high-oleic-acid peanut oil selected by the invention is preferably not less than 70%, and more preferably 75-80%.
In the invention, the OPO is prepared by using oleic acid (derived from edible vegetable oil) as a raw material under the catalysis of enzyme according to the specification of GB 30604-. The oleic acid content in the product obtained by separating the high-oleic-acid peanut oil after hydrolysis reaches over 75 percent, so that the high-oleic-acid peanut oil is suitable for being mixed with palm stearin and Sn-1, 3-bit special lipase after hydrolysis and then carrying out ester exchange reaction to obtain the mixed ester rich in OPO structural fat.
After the reaction product is obtained, the invention preferably mixes the obtained reaction product, palm stearin and Sn-1, 3-bit specific lipase and then carries out ester exchange reaction to obtain the mixed ester rich in OPO structural fat.
In the invention, the temperature of the ester exchange reaction is preferably 50-90 ℃, more preferably 55-70 ℃, and most preferably 60 ℃; the time of the ester exchange reaction is preferably 1 to 6 hours, more preferably 1 to 3 hours, and most preferably 1 hour.
In the present invention, the molar ratio of the reaction product to the palm stearin is preferably 2: 1-6: 1, more preferably 3: 1-5: 1; most preferably 5: 1.
in the present invention, the Sn-1, 3-position specific lipase is preferably Novoxin immobilized lipase 40086, Novoxin immobilized lipase T L IM, immobilized Candida Candida sp.99-125 lipase or immobilized porcine pancreatic lipase.
In the present invention, the mass of the Sn-1, 3-position specific lipase is 2 to 10%, more preferably 5 to 8%, and most preferably 6% of the total mass of the reaction product and Pterocarpus oil.
In the present invention, the transesterification reaction is preferably followed by molecular distillation.
In the invention, the molecular distillation temperature is preferably 150-210 ℃, more preferably 160-200 ℃, and the molecular distillation time is preferably 30-90 min, more preferably 50-80 min.
The invention distills off fatty acid or fatty acid ethyl ester by molecular distillation.
FIG. 1 is a flow chart of a method for preparing a mixed ester of an OPO structure-containing lipid according to the present invention.
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
1) Weighing 2.16g of NaOH in a 1000m L three-neck flask, adding 160g of absolute ethyl alcohol and 432g of high oleic acid peanut oil, magnetically stirring in a 75 ℃ oil bath under the protection of nitrogen for 1.5h, cooling to room temperature, carrying out reduced pressure rotary evaporation to remove excessive ethanol, pouring into a separating funnel, standing for layering, separating out lower-layer sodium hydroxide, glycerol and soap, washing with 50 ℃ distilled water to be neutral, carrying out reduced pressure rotary evaporation to remove water, obtaining a reaction product, namely fatty acid ethyl ester, filling into a 500m L sample bottle, filling nitrogen for protection, and placing into a refrigerator for later use.
2) Weighing the fatty acid ethyl ester and the palm stearin obtained in the step 1) according to the molar ratio of 2:1, 3:1, 4:1, 5:1 and 6:1 respectively, wherein the palm stearin is 20g, 0.0225mol, placing the weighed fatty acid ethyl ester and palm stearin into a 250m L three-neck flask, magnetically stirring in an oil bath (400r/min) until the fatty acid ethyl ester and the palm stearin are completely dissolved, adding Novozyme40086 lipase accounting for 8% of the total mass of the fatty acid ethyl ester and the palm stearin, reacting at 70 ℃ for 4h, and distilling to obtain a target product.
Dissolving 50mg of fatty acid ethyl ester in 1m L n-hexane, dropping the solution onto a 20 × 20cm thin-layer chromatographic plate by using a dropping needle, developing the solution by using a developing agent (n-hexane: diethyl ether: glacial acetic acid: 80:20:2, v/v/v), taking out the developed solution after the development is completed, drying the developed solution, developing the developed solution by using 2 ', 7' -dichlorofluorescein, taking a triglyceride strip, carrying out simple methyl esterification, and carrying out gas phase analysis.
Analyzing the relative content of each fatty acid in the fatty acid ethyl ester by using an area normalization method, and calculating the relative content of the fatty acid according to a formula (1):
FIG. 2 is a gas chromatogram of the fatty acid composition of the fatty acid ethyl ester obtained in example 1.
Table 1 shows the fatty acid composition and relative content of the fatty acid ethyl esters obtained in example 1.
Table 1 fatty acid and relative content of fatty acid ethyl ester obtained in example 1
C16:0 represents palmitic acid; c18:0 is stearic acid; c18:1 is oleic acid; c18:2 is linoleic acid; c20:0 is arachidic acid; c20:1 is arachidonic acid; c22:0 is behenic acid; c22:1 is erucic acid; c24:0 is pyroligneous acid.
As shown in the figure 2 and the table 1 in combination with the formula (1), the high oleic acid peanut oil fatty acid ethyl ester has the oleic acid content as high as 78.08 percent and can be used as an ideal raw material for synthesizing OPO.
Table 2 shows physical and chemical indexes of the fatty acid ethyl esters obtained in example 1.
TABLE 2 physicochemical indices of fatty acid ethyl esters obtained in example 1
As is clear from Table 2, the fatty acid ethyl esters obtained in example 1 have good physical and chemical properties and are ideal as raw materials for the synthesis of OPO.
FIG. 3 is a graph showing the effect of the molar ratio of fatty acid ethyl esters and palm stearin in example 1 on the synthesis.
As can be seen from FIG. 3, in the process of increasing the substrate molar ratio from 2:1 to 6:1, the content of OPO and the content of palmitic acid at the 2-position account for all the palmitic acid, which are increased and then stabilized, and the content of palmitic acid, which is decreased and then stabilized; the substrate molar ratio is increased from 2:1 to 5:1, the OPO content is obviously increased, because the oleic acid concentration is increased, and the reaction is promoted to proceed in the positive reaction direction; when the substrate molar ratio is continuously increased to 6:1, the content of the synthesized OPO has no significant change and is stabilized at about 41.14%, the 2-position palmitic acid accounts for about 48% of all the palmitic acid content, the palmitic acid content is stabilized at about 4.7%, and excessive ethyl oleate is not beneficial to product separation, and the production cost is increased, so the optimal selection of the substrate molar ratio is 5: 1.
Example 2
The molar ratio of the fatty acid ethyl ester to the palm hard ester is 5:1, and the ester exchange reaction time is 30min, 1h, 2h, 4h and 6h respectively. Other reaction conditions were the same as in example 1. Obtaining the target product.
FIG. 4 is a graph showing the effect of the transesterification reaction time on the synthesis in example 2.
As can be seen from FIG. 4, when the reaction time is increased to 6 hours at 30min, the content of OPO and palmitic acid at the 2-position in all the palmitic acid content is increased and then decreased, and the content of palmitic acid triglyceride is decreased and then stabilized. When the reaction time is increased to 1h from 30min, the reaction is carried out in the positive reaction direction, the reaction is more sufficient, the content of the target product is obviously increased, the reaction reaches the balance in 1h, the content of OPO is 44.07%, the content of 2-palmitic acid accounts for 56.29% of all the palmitic acid, the content of both palmitic acid is the maximum value, and the content of the palmitic acid is 6.07%; during the reaction time of 1-4 h, with the increase of the reaction time, the OPO is subjected to acyl transfer in the reaction process, the content of byproducts is increased, the content of 2-bit palmitic acid in all palmitic acid is obviously reduced, and the content of palmitic acid is not obviously changed; when the reaction time is increased from 4h to 6h, the by-products produced by acyl transfer react with the palm stearin under the catalysis of the Sn-1, 3-site lipase, so that the content of OPO and the content of 2-site palmitic acid which is all palmitic acid are obviously reduced. The method has the advantages of short reaction time and high economic benefit, ensures the product yield, can better save power and energy, and optimally selects the reaction time to be 1h in consideration of the product yield and the power saving.
Example 3
Mixing the fatty acid ethyl ester obtained in the step 1) of the example 1 with palm stearin according to a molar ratio of 5:1, respectively adding 2%, 4%, 6%, 8% and 10% of Novozyme40086 lipase by mass fraction based on the total mass of the fatty acid ethyl ester and the palm stearin, and carrying out transesterification reaction at 70 ℃ for 1 h. The other conditions were the same as in example 1 to obtain the desired product.
FIG. 5 is a graph showing the effect of enzyme content on the synthesis in example 3. As can be seen from FIG. 5, in the process of increasing the enzyme amount from 2% to 10%, the content of OPO and the content of palmitic acid at 2-position in all the palmitic acid contents are increased and then stabilized, and the content of palmitic acid is decreased and then stabilized; as the enzyme adding amount is increased from 2% to 6%, the contact area between the enzyme and the substrate is increased, the positive reaction process is accelerated, the reaction is more sufficient, and the content of the target product is obviously increased; with the increase of the enzyme adding amount to 10%, the OPO content has no significant change and is stabilized at about 44.11%, the content of the 2-position palmitic acid accounts for about 56.37% of the total palmitic acid content, and the palmitic acid content is stabilized at about 5.96%. This is because when the amount of enzyme is increased to a certain value, the reaction goes into a steady state, and at the same time, an excess amount of lipase increases the rate of the reverse reaction. The proper amount of lipase can reduce the generation of by-products and reduce the production cost on the premise of ensuring the reaction rate. The enzyme addition amount of the reaction is optimally selected to be 6 percent in comprehensive consideration.
Example 4
The fatty acid ethyl ester obtained in step 1) of example 1 and palm stearin were mixed at a molar ratio of 5:1, and Novozyme40086 lipase having a mass fraction of 6% of the total mass of the fatty acid ethyl ester and palm stearin was added to react at 50 ℃, 60 ℃, 70 ℃, 80 ℃ and 90 ℃ for 1 hour, respectively, under the same conditions as in example 1. Obtaining the target product.
FIG. 6 shows the effect of the transesterification temperature on the synthesis in example 4. As can be seen from fig. 6, the OPO content increases and then decreases during the temperature increase from 50 ℃ to 90 ℃, the palmitic acid in the 2-position accounts for the total palmitic acid content, tends to stabilize and then decreases, and the palmitic acid triglyceride content decreases and then increases. When the temperature is increased from 50 ℃ to 60 ℃, the palm stearin is completely dissolved, the intersolubility of the palm stearin and the ethyl oleate is increased, the enzyme and a reaction substrate are fully mixed, the positive reaction rate is increased, and the content of OPO is obviously increased. Is (46.32 +/-0.03)%, the content of palmitic acid triglyceride is obviously reduced; the content of OPO is about 43.64 percent, the content of 2-site palmitic acid is about 56.58 percent of all palmitic acid, and the content of palmitic acid is about 6.25 percent when the temperature is increased from 60 ℃ to 80 ℃. And when the temperature is continuously increased, the stability of partial enzyme is damaged, the acyl migration in the lipase catalytic reaction is enhanced, the content of OPO and the content of palmitic acid at the 2-position in all the palmitic acid are obviously reduced, and the content of palmitic triglyceride is obviously increased. According to the requirements of the use of the Novozyme40086 enzyme, we chose the optimal reaction temperature of 60 ℃.
Example 5
The fatty acid ethyl ester obtained in step 1) of example 1 was mixed with palm stearin at a molar ratio of 5:1, wherein the palm stearin was 20g and 0.0225mol, and Novozyme40086 lipase having a mass fraction of 8% of the total mass of the fatty acid ethyl ester and the palm stearin was added to react at 70 ℃ for 2 hours under the same conditions as in example 1. Obtaining the target product.
The target product obtained in example 5 was analyzed by thin layer analysis, and the results are shown in FIG. 7. The right side is a standard of the mixture of glycerol ester and ethyl oleate and the left side is the target product obtained in example 5.
FIG. 8 is a gas chromatogram of the objective product obtained in example 5.
Table 3 shows the composition and relative content of the objective product obtained in example 5.
TABLE 3 composition and relative content of the target product obtained in example 5
As is clear from fig. 7, fig. 8 and table 3, the contents of fatty acids and ethyl esters in the target product obtained in example 5 were very small, and most of the fatty acids and ethyl esters were diglycerides and triglycerides.
FIG. 9 is a gas chromatogram of the triglyceride composition of the objective product obtained in example 5.
Table 4 shows the composition and relative content of triglycerides of the objective product obtained in example 5.
TABLE 4 composition and relative content of triglycerides of the desired product obtained in example 5
As can be seen from fig. 9 and table 4, the analysis of the triglyceride composition by gas chromatography showed that the relative content of C52, compared with the national standard (C52 is 40%) and the results of some researchers (C52 is about 40%), showed that the target product obtained in example 5 had a high content of OPO structural lipid and a low content of residual palmitic acid triglyceride, and satisfied the national standard requirements.
FIG. 10 is a gas chromatogram of the fatty acid composition of the triglyceride in the objective product obtained in example 5.
Table 5 shows the triglyceride-like fatty acid composition and relative content in the target product obtained in example 5.
Table 5 triglyceride-like fatty acid composition and content in objective product obtained in example 5
FIG. 11 is a gas chromatogram of the Sn-2 fatty acid composition in triglycerides of the target product obtained in example 5;
table 6 shows the composition and content of Sn-2 fatty acid in triglyceride of the objective product obtained in example 5.
TABLE 6 fatty acid composition and relative content of Sn-2 in triglycerides of the target products obtained in example 5
As is clear from fig. 10, table 5, fig. 11 and table 6, in example 5, when the reaction temperature was 60 ℃, the sn-2 palmitic acid content of the target product was 58.3%, the total oleic acid content was 52.2%, and the oleic acid insertion rate was high.
FIG. 12 is a graph showing the SFC of the objective product obtained in example 5 as a function of temperature.
As can be seen from FIG. 12, the SFC of the target product rapidly decreased from 10 to 30 ℃ and the SFC of OPO decreased from 30.968% to 2.874%, indicating that the melting point of the triglycerides constituting the OPO was concentrated between 10 and 30 ℃ and the range of the melting point of the monounsaturated triglycerides was (1 to 23 ℃). The target product still contains a small amount of palm stearin with a high melting point, so that the target product still contains a very small amount of solid fat between 30 ℃ and 45 ℃, and the content of the solid fat is about 0.203%.
In summary, the physicochemical indices of the target product obtained in example 5 are shown in table 7.
TABLE 7 physicochemical indices of the target products obtained in example 5
As can be seen from Table 7, the target product obtained in example 5 is a mixed ester rich in OPO structural ester and meets the national standards.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Example 6
Weighing the high-oleic-acid peanut oil free fatty acid and palm stearin obtained by medium-pressure hydrolysis according to a molar ratio of 6:1, wherein the palm stearin accounts for 20g and is 0.0225mol, placing the weighed free fatty acid and palm stearin into a 250m L three-neck flask, magnetically stirring in an oil bath (400r/min) until the materials are completely dissolved, adding Novozyme40086 lipase which accounts for 10% of the total mass of the free fatty acid and the palm stearin, reacting at 70 ℃ for 4h, and distilling to obtain a target product.
FIG. 13 is a gas chromatogram of the triglyceride composition of the objective product obtained in example 6.
Table 8 shows the composition and relative content of triglycerides of the objective product obtained in example 6
TABLE 8 composition and relative content of triglycerides of the desired product obtained in example 6
As can be seen from fig. 13 and table 8, the content of OPO structural lipid of the target product obtained in example 6 is greater than 40%, and the content of the remaining palmitic acid triglyceride is low, which meets the national standard.
FIG. 14 is a gas chromatogram of the fatty acid composition of the triglyceride in the objective product obtained in example 6.
Table 9 shows the triglyceride-like fatty acid composition and relative content in the target product obtained in example 6.
Table 9 triglyceride-like fatty acid composition and content in objective product obtained in example 6
FIG. 15 is a gas chromatogram of the fatty acid composition of the triglyceride Sn-2 in the objective product obtained in example 6.
Table 10 shows the composition and relative content of Sn-2 fatty acid in triglyceride of the objective product obtained in example 6.
TABLE 10 fatty acid composition and relative content of Sn-2 in triglycerides of the target products obtained in example 6
As is clear from fig. 14, fig. 15, table 10 and table 10, the target product obtained in example 6 had a sn-2 palmitic acid content of 55.89% and a total oleic acid content of 50.18%.
In summary, the physicochemical indices of the target product obtained in example 6 are shown in table 11.
TABLE 11 physicochemical indices of the target products obtained in example 6
As can be seen from fig. 11, the target product obtained in example 6 is a mixed ester rich in OPO structural ester and meets the national standards.
The above is only one embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (3)
1. A preparation method of mixed ester rich in OPO structure ester comprises the following steps:
1) carrying out alcoholysis reaction or medium-pressure hydrolysis reaction on the high-oleic-acid peanut oil to obtain a reaction product; the oleic acid content of the high-oleic-acid peanut oil is more than or equal to 70 percent; the reaction product of the alcoholysis reaction is fatty acid ethyl ester, and the reaction product of the medium-pressure hydrolysis reaction is fatty acid; the alcoholysis temperature is 60-80 ℃, and the alcoholysis time is 1-3 h;
the medium-pressure hydrolysis temperature is 240-260 ℃; the water adding amount is 1-1.2 times of that of the grease; the pressure of the medium-pressure hydrolysis is 24-28 kg/cm2；
2) Mixing the reaction product obtained in the step 1), palm stearin and Sn-1, 3-bit specific lipase, and then carrying out ester exchange reaction to obtain a mixed ester rich in OPO structural fat;
the temperature of the ester exchange reaction is 50-90 ℃, and the time of the ester exchange reaction is 1-6 h; the molar ratio of the reaction product to the palm stearin is 2: 1-6: 1; the mass of the Sn-1, 3-bit specific lipase is 2-10% of the total mass of the reaction product and the palm stearin.
2. The preparation method of claim 1, wherein the time of the medium-pressure hydrolysis in the step 1) is 8-10 h.
3. The process according to claim 1, wherein the Sn-1, 3-position specific lipase in the step 2) is Novoxin immobilized lipase 40086, Novoxin immobilized lipase T L IM, immobilized Candida Candidasp.99-125 lipase or immobilized porcine pancreatic lipase.
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