CN103060394A - Method of glycerolysis reaction for preparing partial glyceride - Google Patents
Method of glycerolysis reaction for preparing partial glyceride Download PDFInfo
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- 239000000706 filtrate Substances 0.000 claims description 9
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 8
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- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
The invention discloses a method of glycerolysis reaction for preparing partial glyceride, and belongs to the technical field of oil modification. The method comprises a first step of immobilization of Lipase T1, a second step of glycerolysis reaction of immobilized lipase catalysis oil, and a third step of separating products. The Lipase T1 is high in thermostability, after being immobilized through hydrophobicity macroreticular resin, the Lipase T1 can catalyze glycerolysis to be reacted under no-water environment in range of 75-95 DEG C. No by-product is produced, content of the partial glyceride is high in the products, immobilized enzyme can be recycled, and therefore the method of the glycerolysis reaction for preparing the partial glyceride has good application prospect in industries.
Description
Technical field
The present invention relates to a kind of grease production method that is rich in partial glyceride.
Background technology
Partial glyceride is the general designation of direactive glyceride and triglyceride, and triglyceride and direactive glyceride all are very important foodstuff additive.Direactive glyceride is widely used in fields such as food, pharmacy, cosmetic industries as a kind of important emulsifying agent.The functional edible oil of triglyceride is the new oil that forms take natural edible oil as raw material, by the biological enzyme modification, have clear and definite function and the edible safeties such as obesity, reducing blood-fat of preventing, as the regeneration product of oil with common edible, can fundamentally solve because the lipid excess accumulation that the excess ingestion of grease causes in the prerequisite that does not change existing food habits.The production of partial glyceride can be divided into chemical method and enzyme process by the difference of catalyzer.Chemical method has the shortcomings such as energy consumption is large, reaction product is easily degraded, separating-purifying difficulty, is unsuitable for the production of unsaturated fatty acids partial glyceride.Utilize preparing diglyceride by enzyme catalysis, owing under mild conditions, reacting, not only can reduce the consumption of energy and production technique to the impact of environment, can also obtain producing the product that color, local flavor, mouthfeel etc. all have better quality; What is more important, because biological activity and the specific selectivity high (solid and position) of lipase, the side reaction of enzyme process glycerolysis reaction is few, can obtain the partial glyceride product of ad hoc structure.
From the reaction mechanism of lipase, the preparation method of partial glyceride mainly contains glycerine and fatty acid esterification method, the partial hydrolysis method of natural fats and oils and glycerine solution.Lipid acid and glycerine carry out esterification under catalyst action can obtain direactive glyceride, triglyceride, also may obtain by-product glycerin three esters simultaneously.But, owing to glycerine and lipid acid generally are that highly pressured hydrolysis preparation through natural fats and oils comes, passing through again the enzyme process esterification take the two as raw material and prepare triglyceride, this operational path is more much higher than grease glycerine solution on production cost.The operational path of the synthetic partial glyceride of the enzymatic hydrolysis method of triglyceride level has obvious drawback when mass-producing is used, at first, hydrolysis reaction produces a large amount of by product free fatty acids and a certain amount of glycerine; Secondly, direactive glyceride and the triglyceride yield in hydrolysate is lower.Glycerine and triglyceride level can generate direactive glyceride and triglyceride in lipase-catalyzed lower reaction, and every mole of grease can generate the direactive glyceride of 3mol or the triglyceride of 1.5mol in theory.Compare the method for other several production partial glycerides, it is extensive that glycerine solution approach has raw material sources, easily obtain, and substrate utilization efficient advantages of higher, therefore a lot of scholars start with from glycerolysis reaction, the industrial method of research Production by Enzymes partial glyceride.But because the higher viscosity of the not mutual solubility of glycerine and grease and solvent-free reaction system, enzymatic glycerolysis reaction is difficult to effectively carry out; Although by adding organic solvent and keeping the certain water content of reaction system can promote the carrying out of glycerolysis reaction, but organic solvent brings cost pressure can for follow-up solvent recuperation and have the danger of dissolvent residual, and the moisture in the reaction system can cause the hydrolysis of grease, produces the lipid acid that is difficult to separate with direactive glyceride.Patent CN100376541C provides a kind of method of enzyme process glycerine solution synthetic triglyceride, the method adds hydrophilic carrier silica gel as sorbent material in being added with the reactive system of glycerine so that glycerine forms ADSORPTION STATE, thereby overcome glycerine to the parcel of enzyme and the series of problems that brings, improved the catalytic effect of lipase.Although the method has been improved the speed of response of enzyme process glycerine solution greatly, exist silica gel to be difficult to the shortcomings such as regeneration with stirring difficulty, the silica gel that immobilized enzyme can't separate, the silica gel automatic bonding brings, the difficulty of industrialized implementation is very large.Patent CN101397577A provides a kind of method of utilizing preparing diglyceride through continuous glycerolysis by enzyme method, and the method has improved reaction efficiency and enzyme is had provide protection take lower boiling single-phase organic solvent as reaction medium has reduced the reaction viscosity; But the method has been introduced organic solvent in reaction system, and this just need to carry out follow-up solvent recuperation operation, and strictly controls the dissolvent residual in the product.Studies show that of past, lipase-catalyzed a certain amount of water of grease reaction needed, this part water is as substrate or as keeping the necessary water of lipase activity conformation.Patent US6337414B1 provides a kind of and added the enzyme reaction method that water is realized the glycerine solution smoothly in reaction system, owing to having added water in the method, hydrolysis reaction also having occured, produced a large amount of free fatty acidies in the product, has increased the cost of side reaction product separation and the follow-up refining of product.Therefore develop anhydrously, the synthetic partial glyceride of the glycerolysis reaction of solvent-free system can obtain efficiently, the partial glyceride production technique of economy, environmental protection.
Summary of the invention
The object of the invention is to the shortcoming for the prior art existence, utilize macropore low-pole polymeric adsorbent immobilized lipase Lipase T1, provide a kind of immobilized enzyme take hydrophobic material as carrier to make catalyzer, the method that partial glyceride is produced in the reaction of catalyzing glycerol solution under anhydrous, solvent-free system, the method do not have lipid acid to produce.The glycerine hydrolysis products can obtain direactive glyceride and be rich in the oil and fat product of triglyceride behind molecular distillation, simplified the technique of follow-up separation.
The present invention is achieved through the following technical solutions for achieving the above object:
A kind of glycerolysis reaction prepares the method for partial glyceride, comprises the steps:
(1) immobilization of lipase Lipase T1: the free-fat enzyme LipaseT1 that gets 5 ~ 10 parts of pretreated low-pole macroporous adsorbent resins of quality, the Tris-HCl damping fluid of 10 ~ 20 parts of quality, 0.1 ~ 1 part of quality mixes, 25 ~ 35 ℃ of lower whip attachment 1 ~ 2 hour, then filter and be dried to moisture content and be not higher than 1%, obtain the immobilized lipase LipaseT1 of hydrophobic resin;
(2) fixed lipase catalyzed grease glycerolysis reaction: the glycerine mixing of getting the vegetables oil of 10 parts of quality, 1 ~ 4 part of quality is added to head tank, the rear constantly packed column by immobilized lipase LipaseT1 is housed and loop back head tank stirs, whole reactive system places the vacuum system of 10 ~ 500Pa lower, 75 ~ 95 ℃ of lower reactions 2 ~ 6 hours, get product mixtures;
(3) separate: described product mixtures obtains upper oil phase and is the grease that is rich in partial glyceride through centrifugation, separates the product that obtains direactive glyceride and be rich in triglyceride through molecular distillation again.
Preferably, the pretreatment technology of macroporous adsorbent resin is described in the step (1): with 95% alcohol immersion 24h, be washed to the filtrate muddiness that is not white in color; HCl solution soaking 2h with 5% is washed to filtrate and is neutral; Again with 2% NaOH solution soaking 2h, be washed to filtrate and be neutral and get final product.
Preferably, the Tris-HCl buffer concentration in the described step (1) is 0.05mol/L, and pH is 8.8.
Preferably, the moisture content in the described reaction system of step (2) is no more than 0.1%.
Preferably, the loadings of the described immobilized lipase LipaseT1 of step (2) is 1 ~ 10% of reaction raw materials quality.
Preferably, described vegetables oil comprises one or more the mixture in soybean oil, rapeseed oil, peanut oil, Semen Maydis oil, sunflower seed oil, plam oil, palm-kernel oil, Oleum Cocois, oleum lini, sesame oil, camellia seed oil, the sweet oil.
Well-known lipase has the interface and activates phenomenon, in the polarity environment in the active centre of lipase by one movably " lid " cover, and " lid " opening at the interface at substrate and water, thereby come out in the active centre of enzyme, substrate can enter into this center and react.The mode that different lipase " lid " is opened may be different, Lipase T1 lipase has two " lid " structures, one is hydrophobic α 6 spirals, and one is α 7 spirals of half hydrophobic semi-hydrophilic, opens mechanism for its lid at present and also is in the research.This seminar research find with after the Lipase T1 immobilization when self water content is not higher than 1%, the glycerolysis reaction system that is used for water content extremely low (below 0.1%), glycerolysis reaction efficient is very high and do not produce free fatty acids, this may with the double-canopy minor structure of its uniqueness and lid to open mechanism relevant.With respect to the commercial immobilized lipases (water content 2 ~ 5%) that use in a large number at present, take hydrophobicity macropore low-pole polymeric adsorbent as carrier immobilized lipase Lipase T1 than low water content the time, can the efficient catalytic glycerolysis reaction, for the research of glycerolysis reaction, this is beyond thought with respect at present.By lipase and the lipase carrier of selecting to suit, the suitable reaction parameter of employing can be so that the glycerolysis reaction of grease effectively carries out under anhydrous solvent-free system.
With respect to prior art, beneficial effect of the present invention is:
(1) thermostability of the used lipase LipaseT1 of the present invention is high, and adopting can be in 75 ~ 95 ℃ scope after the immobilization of hydrophobicity macroporous adsorbent resin, catalyzing glycerol solution reaction under utmost point low water content, the solvent-free environment; Avoid the generation of the side reactions such as hydrolysis of grease, simplified the recovery of reaction product and follow-up separating technology.
(2) the present invention carries out glycerolysis reaction in solvent-free system, little water surrounding, and glycerolysis reaction efficient is high, does not produce free fatty acids, do not produce by product, partial glyceride content is high in the product, and immobilized enzyme can reuse, so present method has a good application prospect industrial.
Description of drawings
Fig. 1 is a kind of device schematic diagram that enzyme reactor catalysis grease glycerolysis reaction used in the present invention is produced partial glyceride.
Wherein head tank 1, agitator motor 2, under meter 3, pump 4, packed bed enzyme reactor 5 are connected with tensimeter and are connected successively by pipeline.
Embodiment
Introduce in more detail by the following examples enforcement of the present invention.In described embodiment, all per-cents all in mass.
The pretreatment technology of hydrophobicity macroporous adsorbent resin is: with 95% alcohol immersion 24h, wash 2 times to the filtrate muddiness that is not white in color; HCl solution soaking 2h with 5% is washed to filtrate and is neutral; With 2% NaOH solution soaking 2h, be washed to filtrate and be neutral again, 4 ℃ of refrigerators are deposited for subsequent use.
Get the macropore low-pole polymeric adsorbent AB-8 of the activated processing of 500g, Tris-HCl damping fluid (the concentration 0.05mol/L of 1000g, pH8.8), the free-fat enzyme Lipase T1(Leow TC of 20g, RahmanRNZRA, Basri M, Salleh AB.High level expression of thermostable lipase fromGeobacillus sp.strain T1[J] .Bioscience, biotechnology, and biochemistry 2004; 68 (1): 96-103.) mix, 30 ℃ of lower whip attachment 1 hour, then filter, vacuum-drying to moisture content is 0.5%, gets the immobilized lipase Lipase of macroporous adsorbent resin T1, and 4 ℃ of Refrigerator stores are for subsequent use.9Kg purified soyabean oil and 1Kg glycerine are added in the head tank 1, moisture content in the control reaction system is no more than 0.1%, in the situation that magnetic agitation, as shown in Figure 1, reactant is got back in the head tank 1 behind enzyme reactor 5 through pump 4 transportation flows, the consumption of immobilized lipase LipaseT1 is 300g, temperature of reaction is 80 ℃, it is under the vacuum state of 100Pa that whole reactive system places pressure, stopped reaction after 4 hours, reaction product are got upper oil phase after centrifugal and are carried out compositional analysis, and content of triglyceride is 17.5%, diglyceride content is 55.2%, and the content of direactive glyceride is 27.3%.Oil phase is carried out molecular distillation, the direactive glyceride in the separating mixture, direactive glyceride is 97.6% in the lighting end that obtains, triglyceride is 2.3%; Triglyceride level is 35.1% in the heavy phase, and triglyceride is 64.8%.
Embodiment 2
Get the macropore low-pole polymeric adsorbent AB-8 of the activated processing of 500g, Tris-HCl damping fluid (the concentration 0.05mol/L of 1000g, pH8.8), the free-fat enzyme Lipase T1 of 20g mixes, 30 ℃ of lower whip attachment 1 hour, then to filter, vacuum-drying to moisture content is 0.5%, get the immobilized lipase Lipase of macroporous adsorbent resin T1,4 ℃ of Refrigerator stores are for subsequent use.9Kg purified soyabean oil and 1.84Kg glycerine are added in the head tank 1, moisture content in the control reaction system is no more than 0.1%, in the situation that magnetic agitation, as shown in Figure 1, reactant is got back in the head tank 1 behind enzyme reactor 5 through pump 4 transportation flows, the consumption of immobilized lipase LipaseT1 is 300g, temperature of reaction is 80 ℃, it is under the vacuum state of 50Pa that whole reactive system places pressure, stopped reaction after 6 hours, reaction product are got upper oil phase after centrifugal and are carried out compositional analysis, and content of triglyceride is 12.6%, diglyceride content is 55.9%, and the content of direactive glyceride is 31.5%.Oil phase is carried out molecular distillation, the direactive glyceride in the separating mixture, direactive glyceride is 97.5% in the lighting end that obtains, triglyceride is 2.4%; Triglyceride level is 19.1% in the heavy phase, and triglyceride is 70.4%.
Get the macropore low-pole polymeric adsorbent AB-8 of the activated processing of 5Kg, Tris-HCl damping fluid (the concentration 0.05mol/L of 10Kg, pH8.8), the free-fat enzyme Lipase T1 of 100g mixes, 25 ℃ of lower whip attachment 1 hour, then to filter, vacuum-drying to moisture content is 0.6%, get the immobilized lipase Lipase of macroporous adsorbent resin T1,4 ℃ of Refrigerator stores are for subsequent use.90Kg purified soyabean oil and 18.4Kg glycerine are added in the head tank 1, moisture content in the control reaction system is no more than 0.1%, in the situation that magnetic agitation, as shown in Figure 1, reactant is got back to after pump delivery is flowed through enzyme reactor in the head tank 1, the consumption of immobilized lipase LipaseT1 is 3Kg, temperature of reaction is 80 ℃, it is under the vacuum state of 50Pa that whole reactive system places pressure, stopped reaction after 6 hours, reaction product are got upper oil phase after centrifugal and are carried out compositional analysis, and content of triglyceride is 13.7%, diglyceride content is 53.1%, and the content of direactive glyceride is 33.2%.Oil phase is carried out molecular distillation, the direactive glyceride in the separating mixture, direactive glyceride is 98.1% in the lighting end that obtains, triglyceride is 1.7%; Triglyceride level is 21.2% in the heavy phase, and triglyceride is 68.4%.
Embodiment 4
Get the macropore low-pole polymeric adsorbent AB-8 of the activated processing of 500g, Tris-HCl damping fluid (the concentration 0.05mol/L of 1000g, pH8.8), the free-fat enzyme Lipase T1 of 20g quality mixes, 30 ℃ of lower whip attachment 1 hour, then to filter, vacuum-drying to moisture content is 0.5%, get the immobilized lipase Lipase of macroporous adsorbent resin T1,4 ℃ of Refrigerator stores are for subsequent use.9Kg purified soyabean oil and 1.84Kg glycerine are added in the head tank 1, moisture content in the control reaction system is no more than 0.1%, in the situation that magnetic agitation, as shown in Figure 1, reactant is got back to after pump delivery is flowed through enzyme reactor in the head tank 1, the consumption of immobilized lipase LipaseT1 is 300g, temperature of reaction is 80 ℃, it is under the vacuum state of 500Pa that whole reactive system places pressure, stopped reaction after 6 hours, reaction product are got upper oil phase after centrifugal and are carried out compositional analysis, and content of triglyceride is 19.6%, diglyceride content is 51.8%, and the content of direactive glyceride is 28.6%.Oil phase is carried out molecular distillation, the direactive glyceride in the separating mixture, direactive glyceride is 97.7% in the lighting end that obtains, triglyceride is 2.1%; Triglyceride level is 28.2% in the heavy phase, and triglyceride is 71.7%.
Claims (6)
1. a glycerolysis reaction prepares the method for partial glyceride, it is characterized in that, comprises the steps:
(1) immobilization of lipase Lipase T1: the free-fat enzyme LipaseT1 that gets 5 ~ 10 parts of pretreated low-pole macroporous adsorbent resins of quality, the Tris-HCl damping fluid of 10 ~ 20 parts of quality, 0.1 ~ 1 part of quality mixes, 25 ~ 35 ℃ of lower whip attachment 1 ~ 2 hour, then filter and be dried to moisture content and be not higher than 1%, obtain the immobilized lipase LipaseT1 of hydrophobic resin;
(2) fixed lipase catalyzed grease glycerolysis reaction: the glycerine mixing of getting the vegetables oil of 10 parts of quality, 1 ~ 4 part of quality is added to head tank, the rear constantly packed column by immobilized lipase LipaseT1 is housed and loop back head tank stirs, whole reactive system places the vacuum system of 10 ~ 500Pa lower, 75 ~ 95 ℃ of lower reactions 2 ~ 6 hours, get product mixtures;
(3) separate: described product mixtures obtains upper oil phase and is the grease that is rich in partial glyceride through centrifugation, separates the product that obtains direactive glyceride and be rich in triglyceride through molecular distillation again.
2. method according to claim 1 is characterized in that, the pretreatment technology of macroporous adsorbent resin is described in the step (1): with 95% alcohol immersion 24h, be washed to the filtrate muddiness that is not white in color; HCl solution soaking 2h with 5% is washed to filtrate and is neutral; Again with 2% NaOH solution soaking 2h, be washed to filtrate and be neutral and get final product.
3. method according to claim 1 is characterized in that, the Tris-HCl buffer concentration in the described step (1) is 0.05mol/L, and pH is 8.8.
4. method according to claim 1, the moisture content in the described reaction system of step (2) is no more than 0.1%.
5. according to claim 1 and 2 or 3 or 4 described methods, the loadings of the described immobilized lipase LipaseT1 of step (2) is 1 ~ 10% of reaction raw materials quality.
6. according to claim 1 and 2 or 3 or 4 described methods, described vegetables oil comprises one or more the mixture in soybean oil, rapeseed oil, peanut oil, Semen Maydis oil, sunflower seed oil, plam oil, palm-kernel oil, Oleum Cocois, oleum lini, sesame oil, camellia seed oil, the sweet oil.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104388483A (en) * | 2014-11-17 | 2015-03-04 | 深圳清华大学研究院 | Method for preparing diglyceride through solventless continuous enzymolysis |
| CN104830920A (en) * | 2015-04-09 | 2015-08-12 | 华南理工大学 | Method for producing diglyceride |
| CN107540485A (en) * | 2017-08-22 | 2018-01-05 | 福建达安能源实业有限责任公司 | A kind of biology enzyme is used for emulsion and preparation method |
| CN110894515A (en) * | 2019-11-11 | 2020-03-20 | 南昌大学 | Method for synthesizing diglyceride in reverse micelle enzyme system |
| CN112852892A (en) * | 2020-07-29 | 2021-05-28 | 华南理工大学 | Method for preparing partial glyceride through glycerolysis reaction |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104388483A (en) * | 2014-11-17 | 2015-03-04 | 深圳清华大学研究院 | Method for preparing diglyceride through solventless continuous enzymolysis |
| CN104830920A (en) * | 2015-04-09 | 2015-08-12 | 华南理工大学 | Method for producing diglyceride |
| CN104830920B (en) * | 2015-04-09 | 2018-12-11 | 华南理工大学 | A kind of production method of diglyceride |
| CN107540485A (en) * | 2017-08-22 | 2018-01-05 | 福建达安能源实业有限责任公司 | A kind of biology enzyme is used for emulsion and preparation method |
| CN107540485B (en) * | 2017-08-22 | 2019-10-08 | 福建达安能源实业有限责任公司 | A kind of biological enzyme is used for emulsion and preparation method |
| CN110894515A (en) * | 2019-11-11 | 2020-03-20 | 南昌大学 | Method for synthesizing diglyceride in reverse micelle enzyme system |
| CN112852892A (en) * | 2020-07-29 | 2021-05-28 | 华南理工大学 | Method for preparing partial glyceride through glycerolysis reaction |
| CN112852892B (en) * | 2020-07-29 | 2023-04-07 | 华南理工大学 | Method for preparing partial glyceride through glycerolysis reaction |
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