CN104498545A - Preparation method of polyglycerin ester - Google Patents
Preparation method of polyglycerin ester Download PDFInfo
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- CN104498545A CN104498545A CN201410739469.7A CN201410739469A CN104498545A CN 104498545 A CN104498545 A CN 104498545A CN 201410739469 A CN201410739469 A CN 201410739469A CN 104498545 A CN104498545 A CN 104498545A
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Abstract
The invention relates to a method for preparing polyglycerin ester under the catalytic action of immobilized lipase and phospholipase A1. The method specifically comprises the following steps: firstly preparing tripolyglycerol, and then reacting with fatty acid in the presence of the immobilized lipase and the phospholipase A1. The polyglycerin ester is efficiently prepared under a heterogeneous and high-viscosity reaction system; various materials are easy to separate and can be recycled, thus the cost is reduced; the obtained polyglycerin ester is high in yield; the esterification rate can be over 97%; the obtained polyglycerin ester is high in purity; and the content of free fatty acid is smaller than 0.1%.
Description
Technical field
The invention belongs to chemical industry synthesis field, be specifically related to a kind of method that three polyglycerol esters are prepared in immobilized lipase and phospholipase A1 catalysis.
Background technology
Polyglycerol fatty acid ester (being called for short polyglycerol ester, PGFE) is the ester formed by Polyglycerine and lipid acid, and its structure is different according to the difference of the polymerization degree of glycerine, the kind of lipid acid and gamma value thereof.Polyglycerol ester is multi-hydroxy ester class nonionogenic tenside, because its wetting ability strengthens with the increase of the glyceride polymerization degree, lipophilicity is different with the difference of fatty acid ester, so the polymerization degree by changing glycerine, the kind of lipid acid and gamma value, can obtain the tensio-active agent of HLB value by the different performance of 1-16.Between can adjust arbitrarily, therefore O/W type emulsifying agent can be made, also can make w/o type emulsifying agent.Because it is nontoxic, odorless, having biodegradability, is the additive of a class highly effective and safe, food and agricultural organization of united state and the World Health Organization (FAO and WHO) recommendation.
PGFE is the food emulsifier being only second to mono-glycerides, is widely used in bakery product, oleomargarine and beverage, mainly does emulsifying agent, crystal controlling agent, viscosity modifier and starch modifying agent etc.In addition, due to its colorless and odorless, and be not easily hydrolyzed, product appearance, smell are all had no adverse effects, can be composite with other emulsifying agents, there is good synergistic function, therefore its application also progressively expands to daily use chemicals, oil, weaving, medicine and other fields, and produce market capacity is large.And the starting of China's polyglycerol ester industry and development are relatively late, and the hierarchy of skill is relatively low.
Because the purity of PGFE and emulsifying property are determined by the polymerization degree of Polyglycerine and purity to a great extent, therefore synthesize the key that high-quality Polyglycerine is synthesis high quality P GFE.
Wherein, three polyglycerol esters are series products that in polyglycerol ester product, application and development is with the largest potentiality, have been widely used in the fields such as makeup, washing composition, foodstuffs industry and macromolecular material.Three polyglycerol esters are buff powder or granular solids, water insoluble, but are easily scattered in water, are dissolved in ethanol, organic solvent and oils.Belong to nonionogenic tenside, there is high temperature resistant, acidproof feature.HLB value is 7 ~ 8.
The method of synthesizing three Polyglycerine in prior art be all mostly with glycerine be raw material directly shrink polymerization preparation.Because such reaction randomness is comparatively large, selectivity is lower, so just require higher to the selection of catalyzer, causes the increase of production cost, but also have that temperature of reaction is high, energy consumption large and the problem such as environmental pollution.Further, because glycerol molecule has two primary hydroxyls, under acid or alkali exist as catalyzer, polyreaction can proceed down, forms trimerization, four poly-and polyglycerols.Generally we become linear Polyglycerine three Polyglycerine of glycerine primary hydroxyl condensation, but in glycerine process itself, the condensation between primary hydroxyl and secondary hydroxyl can be there is, form branched polyglycerol, or even cyclic polyglycerols, if trimerization glycerin by-product product are more, then potential safety issue is more serious.
Technical at preparation three polyglycerol ester, domestic main employing chemical method.With liquid acid catalysis, efficient synthesis three polyglycerol esters under homogeneous reaction system.Problems existing mainly contains that product purity is low, residual fat acid content is high, shade deviation, have peculiar smell etc., and chemical method synthesis PGFE has the shortcomings such as energy consumption is large, facility investment is many, separating-purifying is difficult.But mainly adopt biological catalysis abroad, mainly with lipase-catalyzed three Polyglycerine and lipid acid or fatty acid methyl ester reaction preparation PGFE.Enzyme process overcomes conventional chemical methods just must can produce PGFE and product purification drawback under high temperature or high pressure; Can react under comparatively mild conditions, reduce side reaction, contribute to improving the quality of products.But this method still needs the problems such as the exploitation of consideration catalyzer cost, catalytic efficiency and novel reactor.There is esterification yield low, the access times of enzyme are low simultaneously, and the technical problem such as the purity of products obtained therefrom is low, becomes main technological difficulties.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of three polyglycerol esters, it is high that the method has productive rate, and cost is low, the advantage that product purity is high.
Technical scheme provided by the invention, is a kind of preparation method of three polyglycerol esters, comprises the steps:
The preparation of the first step three Polyglycerine:
Under vacuum and heating condition, make catalyzer with storng-acid cation exchange resin, glycerine and Racemic glycidol Reactive Synthesis three Polyglycerine;
Concrete, by glycerine and storng-acid cation exchange resin mixing, constant after being heated to 100-120 DEG C, drip Racemic glycidol, keep below vacuum 100pa, more than insulation reaction 2h, after reacting completely, be cooled to less than 80 DEG C, product is shifted out, sealing continues to be cooled to room temperature, filtered and recycled resin, and filtrate is thick trimerization glycerol product, purifying obtains three Polyglycerine, preferably through molecular distillation technique purifying three Polyglycerine;
Wherein, described glycerine and Racemic glycidol mol ratio are 0.9-1.4:2, and optimum mole ratio is 1:2; The consumption of resin is the massfraction that 3 wt%(account for reactant); Vacuum tightness is preferably at 5-50pa.Reaction times is 2-5h, is preferably 3h.
The concrete steps of molecular distillation technique purifying three Polyglycerine are: 1. glycerine is removed in first order molecular distillation: pour thick three Polyglycerine that reaction prepares into storage tank and carry out first order molecular distillation, at below pressure 20pa, knifing rotating speed 250 ± 20 r/min, flow 1-3 drop/sec, condensing temperature 50 ± 5 DEG C, distill under the condition that storage tank temperature is 80 ± 5 DEG C, distill out light phase product and be glycerine.2. secondary molecules distilation trimerization glycerol product: again pour the heavy phase product that distillation obtains into clean storage tank and carry out secondary molecules distillation, at below pressure 20pa, knifing rotating speed 250 ± 10 r/min condition down-off 1-2 drop/sec, condensing temperature 50 ± 5 DEG C, distill under the condition that storage tank temperature is 95 ± 5 DEG C, distilling out light phase product is three Polyglycerine.
Second step prepares three polyglycerol esters: in bubbling style reactor system, lipid acid and step one gained three Polyglycerine prepare three polyglycerol esters under the catalysis of immobilized lipase and phospholipase A1 (Lecitase Ultra), and reacted mixed solution obtains trimerization glyceride mixture and excessive three Polyglycerine through centrifugation;
Wherein, described lipid acid is vegetables oil or animal oil; In order to obtain best quality product, and most suitable productive rate, select the amount of substance proportioning of three Polyglycerine and lipid acid for (1-2): 1, be preferably (1-1.5): 1; Reaction times is 2-6h, and the preferred reaction time is 2.5h; Temperature of reaction is 20-40 DEG C; The airflow rate of bubbling style reactor is 1-3L/min; The mass ratio of immobilized lipase and phospholipase A1 is 1:1; The mass ratio of enzyme concentration and substrate (i.e. lipid acid and three Polyglycerine) is (1-3): 1000.From point of theory, when the amount of substance proportioning of reactant three Polyglycerine and lipid acid is 1:1, the productive rate of three polyglycerol esters is the highest, and (productive rate all calculates with the side that reactant is less, below be not particularly illustrated, all according to said method calculate), when proportioning is near 1:1, productive rate should centered by 1:1, the variation tendency symmetrically reduced.But contriver is found by test of many times, when the amount proportioning of three Polyglycerine and fatty acid material is lower than 1:1, its by product increases, and is not easily separated with finished product, and gained finished product purity is lower, and productive rate is significantly lower; On the contrary when the amount of three Polyglycerine suitable more time, namely when three Polyglycerine and lipid acid are amount of substance proportioning of the present invention, just can obtain higher productive rate, by product is relatively less and be easily separated with finished product, and gained finished product purity is higher.Simultaneously, those skilled in the art know, comparatively lipase is poor for the catalytic effect of phospholipase A1, but price is lower, inventor reduces costs the lipase selecting phospholipase A1 replacement part, but unexpected to find when phospholipase A1 and lipase take mass ratio as 1:1, the lipase of its catalytic effect and equivalent suitable.Enzyme immobilizatio is prior art.Enzyme can be fixed on coating, inorganic particulate (as silicon-dioxide, white carbon black), natural macromolecular material (as ramie, mulberry silk, bamboo fibers), synthesized polymer material (as resin).
3rd step separation and purification: first undertaken dewatering by first order molecular distillation by step 2 gained trimerization glyceride mixture by molecular distillation, degassed, then carries out secondary molecules distillation remaining three Polyglycerine of removing and lipid acid.
Molecular distillation is a kind of difference based on certain temperature and different substances molecular tools under vacuum tightness and realizes the liquid-liquid separation technology that is separated.Its principle of work is under extra-high vacuum degree, according to the difference of mixture molecular tools, is isolated at far below the temperature of its boiling point.Because its separating power not only depends on each component relative volatility of separation mixture, and relevant with the relative molecular mass size of each component, so can be used to be separated the close and system that relative molecular mass is different of volatility.Have service temperature far below boiling point, working pressure is low, heated time is short, separation degree is high advantage.
Compared with prior art, technical scheme of the present invention has following excellent characteristics: compared with prior art, and technical solution of the present invention has following excellent progressive:
(1) the present invention three Polyglycerine green syt new technology is of value to the selectivity and controlling that improve glycerol polymerization reaction, solves low, the shade deviation of product purity, has the shortcomings such as peculiar smell, cyclic polyglycerols content are high, straight chain Polyglycerine content is few.
(2) technical solution of the present invention exploration new way synthesizes three polyglycerol fatty acid esters, adopt direct method reaction preparation three polyglycerol ester, avoid the building-up process of three Polyglycerine mixing intermediate products, thus three polyglycerol fatty acid ester products of high quality, high yield can be obtained.The yield of gained three polyglycerol ester is high, and wherein esterification yield can reach more than 97%; The purity of gained three polyglycerol ester is high, and contained free fatty acids is less than 0.1%.
(3) technical solution of the present invention adopts solvent-free nonhomogeneous system enzyme law catalysis to synthesize control mechanism and the Key Common Technologies of three polyglycerol esters; Adopt bubbling style column type reactor to carry out extension reaction, under heterogeneous, high viscosity reaction system, efficiently synthesize three polyglycerol esters.
(4) technical solution of the present invention nonhomogeneous system efficient catalytic technology, product is easily separated, and immobilized enzyme is reusable, and cost is low, pollutes little.Adopt immobilized enzyme catalysis, use bubbling style column type reactor, will there are three-phase even four phases in reaction system, in thick ester products, content of monoglyceride reaches more than 50%, and immobilized enzyme reuses more than 80 times, and enzymic activity does not significantly decrease.Compared with lipase, phospholipase A1 cheaper, cost advantage is comparatively obvious, and both obtain excellent effect so that the ratio of optimum is used in combination.This system is not subject to the impact of raw material free fatty acid and moisture simultaneously, and cheap waste grease can be utilized to be raw material, as hogwash fat, acidifying wet goods, while reduction production cost, decreases environmental pollution.Residual reactant can return recycle, recycles, thus reduce costs as three Polyglycerine can return.
(5) in technical solution of the present invention with enzyme be catalyzer, little to equipment corrosion, side reaction is few, reaction conditions is gentle, and immobilized enzyme recoverable is easily separated, does not produce waste liquid, and production technique is simple, reduces the investment to equipment.When advocating green chemical industry and energy scarcity, produce with solid acid catalysis the road that three polyglycerol esters provide a Sustainable development undoubtedly.
Embodiment
Further describe the present invention below by way of embodiment, but the present invention is not limited only to following examples.Operative norm GB13510-92.
embodiment 1
By 10kg glycerine and 9g storng-acid cation exchange resin (D001SS large hole strong acid styrene system cation exchange resin), constant after being heated to 110 DEG C, drip 20kg Racemic glycidol, vacuum 10pa is kept to react 3h, after be cooled to less than 80 DEG C, product is shifted out, sealing continues to be cooled to room temperature, filtered and recycled resin, filtrate is thick trimerization glycerol product, pour thick three Polyglycerine that reaction prepares into storage tank and carry out first order molecular distillation, at pressure 15 pa, knifing rotating speed 250 r/min, flow 3 drops/sec, condensing temperature 50 DEG C, distill under the condition that storage tank temperature is 80 DEG C, distill out light phase product and be glycerine, again pour the heavy phase product that distillation obtains into clean storage tank and carry out secondary molecules distillation, at pressure 8pa, knifing rotating speed 250 r/min condition down-off 1 drop/sec, condensing temperature 50 DEG C, distill under the condition that storage tank temperature is 95 DEG C, distilling out light phase product is three Polyglycerine.
In bubbling style reactor system, the airflow rate of bubbling style reactor is 2L/min, at 30 DEG C, the lipid acid of 10kg and above-mentioned obtained 8.4kg tri-Polyglycerine are calculated there is the quality of 25g(by enzyme) under the catalysis of immobilized lipase and phospholipase A1 (mass ratio is 1:1), reaction 2.5h, reacted mixed solution obtains trimerization glyceride mixture and excessive three Polyglycerine through centrifugation; Gained trimerization glyceride mixture is undertaken dewatering by first order molecular distillation, degassed, then carry out secondary molecules distillation remaining three Polyglycerine of removing and lipid acid; The productive rate of gained three polyglycerol ester is that 65.9%(is with fatty acid) purity is 99.0%(wt%) in fatty acid content be 0.5wt%, HLB be 7.0, fusing point is 54.3 DEG C., be qualified product.
Wherein, enzyme immobilizatio step is: the mixed powder (both mass ratioes are 1:1) getting 0.25kg lipase and phospholipase A1, it to be dispersedly dissolved in 1L water, to be stirred to homogeneous phase.In lipase mixed aqueous solution, add 1L polyurethane binder R120 again, fully stir and form soup compound; Dip mixed solution with spread pen, and whole mixing soup compounies is painted on 10*100dm uniformly
2two surfaces up and down of silk base cloth; An angle of fixed base cloth, is placed in shady and cool ventilation place, dries under room temperature.
embodiment 2
By 10kg glycerine and 9g storng-acid cation exchange resin (D001SS large hole strong acid styrene system cation exchange resin), constant after being heated to 110 DEG C, drip 20kg Racemic glycidol, vacuum 10pa is kept to react 3h, after be cooled to less than 80 DEG C, product is shifted out, sealing continues to be cooled to room temperature, filtered and recycled resin, filtrate is thick trimerization glycerol product, pour thick three Polyglycerine that reaction prepares into storage tank and carry out first order molecular distillation, at pressure 15 pa, knifing rotating speed 250 r/min, flow 3 drops/sec, condensing temperature 50 DEG C, distill under the condition that storage tank temperature is 80 DEG C, distill out light phase product and be glycerine, again pour the heavy phase product that distillation obtains into clean storage tank and carry out secondary molecules distillation, at pressure 8pa, knifing rotating speed 250 r/min condition down-off 1 drop/sec, condensing temperature 50 DEG C, distill under the condition that storage tank temperature is 95 DEG C, distilling out light phase product is three Polyglycerine.
In bubbling style reactor system, the airflow rate of bubbling style reactor is 2L/min, at 30 DEG C, the lipid acid of 10kg and above-mentioned obtained 7.6kg tri-Polyglycerine are calculated there is the quality of 25g(by enzyme) (mass ratio is 1:1 for immobilized lipase and phospholipase A1, enzyme immobilizatio step is with embodiment 1) catalysis under, reaction 2.5h, reacted mixed solution obtains trimerization glyceride mixture and excessive three Polyglycerine through centrifugation; Gained trimerization glyceride mixture is undertaken dewatering by first order molecular distillation, degassed, then carry out the secondary molecules distillation remaining Polyglycerine of removing and lipid acid; The productive rate of gained three polyglycerol ester is that 60.2%(is in three Polyglycerine) purity is 99.1%(wt%) in fatty acid content be 0.5wt%, HLB be 7.1, fusing point is 54.3 DEG C, is qualified product.
embodiment 3
By 10kg glycerine and 9g storng-acid cation exchange resin (D001SS large hole strong acid styrene system cation exchange resin), constant after being heated to 110 DEG C, drip 20kg Racemic glycidol, vacuum 10pa is kept to react 2h, after be cooled to less than 80 DEG C, product is shifted out, sealing continues to be cooled to room temperature, filtered and recycled resin, filtrate is thick trimerization glycerol product, pour thick three Polyglycerine that reaction prepares into storage tank and carry out first order molecular distillation, at pressure 10 pa, knifing rotating speed 250 r/min, flow 3 drops/sec, condensing temperature 50 DEG C, distill under the condition that storage tank temperature is 80 DEG C, distill out light phase product and be glycerine, again pour the heavy phase product that distillation obtains into clean storage tank and carry out secondary molecules distillation, at pressure 6 pa, knifing rotating speed 250 r/min condition down-off 2 drops/sec, condensing temperature 50 DEG C, distill under the condition that storage tank temperature is 95 DEG C, distilling out light phase product is three Polyglycerine.
In bubbling style reactor system, the airflow rate of bubbling style reactor is 1L/min, at 30 DEG C, the lipid acid of 10kg and above-mentioned obtained 12.6kg tri-Polyglycerine are calculated there is the gauge of 60g(by enzyme) under the catalysis of immobilized lipase and phospholipase A1 (mass ratio is 1:1), reaction 2h, reacted mixed solution obtains trimerization glyceride mixture and excessive three Polyglycerine through centrifugation; Gained trimerization glyceride mixture is undertaken dewatering by first order molecular distillation, degassed, then carry out secondary molecules distillation remaining three Polyglycerine of removing and lipid acid; The productive rate of gained three polyglycerol ester is that 76.8%(is with fatty acid), purity is 99.5%(wt%), fatty acid content is 0.7wt%, HLB is 7.2, and fusing point is 54.4 DEG C, and product is qualified.
Wherein, enzyme immobilizatio step is: the activation of (1) ramie: the some ramies of clip, the impurity on 0.5 hour removing ramie surface is boiled with 0. 5mo1/ L KOH, then the NaI04 solution oxide of 0.1 mol/L concentration is used, after 6 hours, taking-up deionized water is cleaned, glycerol adding leaves standstill 40 min in ramie surface, to remove unreacted NaIO4, uses deionized water cleaned standby seam.
(2) enzyme liquid preparation: phosphoric acid buffer (the 0. 025mo1/ L a certain amount of porcine pancreatic lipase dry powder being dissolved in 50mL, pH 7.5) in, 4 DEG C of low temperature are even, and centrifugal 10 min under 10000r/min rotating speed, then get supernatant liquor and store in refrigerator for subsequent use.
(3) crosslinked: the ramie that step (1) activates to be placed in the enzyme liquid that Erlenmeyer flask and step (2) obtain and to be cross-linked at 4 DEG C, often crosslinked 35 minutes, shake 15 minutes, react 3 hours.After crosslinked, with deionized water at room temperature repetitive scrubbing immobilized enzyme more than 5 times, with guarantee ramie surface uncrosslinked on resolvase washed down.For improving the degree of crosslinking of aldehyde radical, the method for repeating step (3) is taked repeatedly to be cross-linked.After each taking-up ramie, blot ramie surface-moisture with filter paper, then put into enzyme liquid and be cross-linked.
embodiment 4
Prepare three polyglycerol esters: by 20kg glycerine and 18g storng-acid cation exchange resin (D001SS large hole strong acid styrene system cation exchange resin), constant after being heated to 110 DEG C, drip 40kg Racemic glycidol, vacuum 10pa is kept to react 2h, after be cooled to less than 80 DEG C, product is shifted out, sealing continues to be cooled to room temperature, filtered and recycled resin, filtrate is thick trimerization glycerol product, pour thick three Polyglycerine that reaction prepares into storage tank and carry out first order molecular distillation, at pressure 8 pa, knifing rotating speed 250 r/min, flow 2 drops/sec, condensing temperature 50 DEG C, distill under the condition that storage tank temperature is 80 DEG C, distill out light phase product and be glycerine, again pour the heavy phase product that distillation obtains into clean storage tank and carry out secondary molecules distillation, at pressure 3 pa, knifing rotating speed 250 r/min condition down-off 2 drops/sec, condensing temperature 50 DEG C, distill under the condition that storage tank temperature is 95 DEG C, distilling out light phase product is three Polyglycerine.
In bubbling style reactor system, the airflow rate of bubbling style reactor is 3L/min, at 30 DEG C, the lipid acid of 10kg and above-mentioned obtained 16.8kg tri-Polyglycerine are calculated there is the gauge of 25g(by enzyme) (both mass ratioes are 1:1 for immobilized lipase and phospholipase A1, curing is with embodiment 3) catalysis under, reaction 2.5h, reacted mixed solution obtains trimerization glyceride mixture and excessive three Polyglycerine through centrifugation; Gained trimerization glyceride mixture is undertaken dewatering by first order molecular distillation, degassed, then carry out the secondary molecules distillation remaining Polyglycerine of removing and lipid acid; The productive rate of gained three polyglycerol ester is that 63.7%(is with fatty acid) purity is 98.6%(wt%), fatty acid content is 0.8wt%, HLB is 7.8, and fusing point is 54.3 DEG C, and product is qualified.
Claims (10)
1. a preparation method for three polyglycerol esters, is characterized in that, comprises the steps:
The preparation of the first step three Polyglycerine:
Under vacuum and heating condition, make catalyzer with storng-acid cation exchange resin, glycerine and Racemic glycidol Reactive Synthesis three Polyglycerine;
Second step prepares three polyglycerol esters: in bubbling style reactor system, lipid acid and step one gained three Polyglycerine synthesize three polyglycerol esters under the catalysis of immobilized lipase and phospholipase A1, and reacted mixed solution obtains trimerization glyceride mixture and excessive three Polyglycerine through centrifugation;
Wherein, the proportioning of three Polyglycerine and lipid acid is (1-2): 1; Reaction times is 2-6h; Temperature of reaction is 20-40 DEG C; The mass ratio of immobilized lipase and phospholipase A1 is 1:1;
3rd step separation and purification: first undertaken dewatering by first order molecular distillation by step 2 gained trimerization glyceride mixture by molecular distillation, degassed, then carries out secondary molecules distillation remaining three Polyglycerine of removing and lipid acid, obtains trimerization glyceride product.
2. the preparation method of three polyglycerol esters as claimed in claim 1, it is characterized in that, the concrete steps of step one are by glycerine and storng-acid cation exchange resin mixing, constant after being heated to 100-120 DEG C, drip Racemic glycidol, keep below vacuum 100pa, insulation reaction 2-5h, after reacting completely, be cooled to less than 80 DEG C, product is shifted out, sealing continues to be cooled to room temperature, and filtered and recycled resin, filtrate is thick three Polyglycerine.
3. the preparation method of three polyglycerol esters as claimed in claim 2, is characterized in that, the glycerine described in step one and Racemic glycidol mol ratio are 0.9-1.4:2, the consumption of resin be 3 wt%(its account for the massfraction of reactant); Vacuum tightness is 5-50pa; Reaction times is 3h.
4. the preparation method of three polyglycerol esters as claimed in claim 3, is characterized in that, the mol ratio of glycerine described in step one and Racemic glycidol is 1:2.
5. the preparation method of three polyglycerol esters as claimed in claim 2, it is characterized in that, thick three Polyglycerine before carrying out second step through molecular distillation technique purifying, concrete steps are: 1. glycerine is removed in first order molecular distillation: pour thick three Polyglycerine that reaction prepares into storage tank and carry out first order molecular distillation, at below pressure 20pa, knifing rotating speed 250 ± 20 r/min, flow 1-3 drop/sec, condensing temperature 50 ± 5 DEG C, distill under the condition that storage tank temperature is 80 ± 5 DEG C, distill out light phase product and be glycerine; 2. secondary molecules distilation trimerization glycerol product: again pour the heavy phase product that distillation obtains into clean storage tank and carry out secondary molecules distillation, at below pressure 20pa, knifing rotating speed 250 ± 10 r/min condition down-off 1-2 drop/sec, condensing temperature 50 ± 5 DEG C, distill under the condition that storage tank temperature is 95 ± 5 DEG C, distilling out light phase product is three Polyglycerine.
6. the preparation method of three polyglycerol esters as claimed in claim 1, is characterized in that, the lipid acid described in step 2 is vegetables oil or animal oil.
7. the preparation method of three polyglycerol esters as claimed in claim 1, is characterized in that, the ratio of the amount of substance of three Polyglycerine and lipid acid described in step 2 is (1-1.5): 1.
8. the preparation method of three polyglycerol esters as claimed in claim 1, is characterized in that, in step 2, the mass ratio of enzyme concentration and substrate (i.e. lipid acid and three Polyglycerine) is (1-3): 1000.
9. the preparation method of three polyglycerol esters as claimed in claim 1, is characterized in that, in step 2, the airflow rate of bubbling style reactor is 1-3L/min.
10. the preparation method of three polyglycerol esters as claimed in claim 1, is characterized in that, the reaction times in step 2 is 2.5h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483714A (en) * | 2002-07-15 | 2004-03-24 | ������������ʽ���� | Method for producing fatty acid |
| WO2009043879A1 (en) * | 2007-10-01 | 2009-04-09 | Nestec S.A. | Composition for controlling lipase catalyzed reactions |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483714A (en) * | 2002-07-15 | 2004-03-24 | ������������ʽ���� | Method for producing fatty acid |
| WO2009043879A1 (en) * | 2007-10-01 | 2009-04-09 | Nestec S.A. | Composition for controlling lipase catalyzed reactions |
Non-Patent Citations (1)
| Title |
|---|
| 万分龙 等: "强酸性阳离子交换树脂催化合成高纯度低聚甘油", 《粮食与油脂》 * |
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