CN1074898A - Technology with separating mono fatty acid glyceride by solvent crystallizing method - Google Patents
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- CN1074898A CN1074898A CN 92100594 CN92100594A CN1074898A CN 1074898 A CN1074898 A CN 1074898A CN 92100594 CN92100594 CN 92100594 CN 92100594 A CN92100594 A CN 92100594A CN 1074898 A CN1074898 A CN 1074898A
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Abstract
A kind of technology with separating mono fatty acid glyceride by solvent crystallizing method belongs to the Separation of Organic Compounds field.With the crude product of low-carbon (LC) saturated alcohol dissolving monoglyceride, solid is separated out in cooling, cools off filtrate after the filtration again and separates out monoglyceride, filters out solid and drying, and it is multiplexing that filtrate turns back to dissolution process.This technology can obtain content greater than 90% mono-glycerides product, and yield is greater than 90%, and flow process is simple, pollution-free, be easy to industrialization.
Description
The present invention belongs to the Separation of Organic Compounds field for isolate the technology of Monoethylene Glycol (MEG) product from the primary products (abbreviating thick ester as) of mono fatty acid glycidol (abbreviation mono-glycerides).
Mono-glycerides is the general name of a compounds, and it has two kinds with dividing foreign body object, and structural formula is respectively:
(wherein, the R difference then is different mono-glycerides)
As the important emulsifying agent of a class, mono-glycerides is widely used in foodstuffs industry, daily chemical industry, medicine and Process Technology of Polymer field.
The industrial mono-glycerides primary products of producing are mixtures of mono-glycerides, dialycerides fat acid esters (being called for short two sweet esters), fatty acid triglyceride (abbreviation triglyceride), ester (being grease) and glycerine and lipid acid.Wherein, mono-glycerides 40～60%, two sweet ester 30～45%, triglyceride 5～15%, glycerine 2～10%, free fatty acids or its salt 1～5%.Wherein, mono-glycerides is the effective constituent that the mono-glycerides product uses as emulsifying agent.Therefore, hope can be developed by the mono-glycerides primary products and be isolated the effective way of content of monoglyceride at the product more than 90%.
In the separation of mono-glycerides, unique industrialized method is a molecular distillation at present.Its ultimate principle is under vacuum condition, utilize component of mixture molecular free path difference and separated.
Solvent crystallization also is seen in report in the mono-glycerides Separation Research.
Guia Hill (1971) boils off free glycerol to 60.8% 1-palmitin under 150 ℃ and 0.02mmHg, under 150～160 ℃, 0.008mmHg, distill, the overhead product that obtains is with hexane: ether is that 1: 1 solvent carries out twice crystallization, obtains the 1-hexadecanoic acid direactive glyceride of concentration 〉=99%.Though this method has obtained high-purity mono-glycerides, complex procedures.Need boil off glycerine earlier and product be carried out molecular distillation, the operational condition harshness; And recrystallisation solvent hexane, ether cost an arm and a leg, and make that this technology can't industrialization.
United States Patent (USP) [US.Pat.2,740,799] has been reported with solvent crystallization and has been separated mono-glycerides.Solvent for use is a low-carbon (LC) ketone, and with C
3-C
6Between alkyl ketone be excellent, as acetone, butanone, methyl propyl ketone, methyl butyl ketone, 2-ethyl ketone, second acetone, butyrone etc.Can use single solvent, also available above-mentioned two kinds or multiple solvent are compound.It is fixed that solvent load will come according to the situation of material handling, and the volume ratio of solvent, material (thick ester) is 1/2～5 generally speaking, can arrive 10 sometimes.Basic craft course is: (1) mixes thick ester and selected solvent, makes it form uniform solution (can heat in case of necessity); (2) make the solvent cooling, to a certain degree there being solid to separate out.When cold analysis temperature that solution is cooled to design, make solid-liquid separation (available centrifugal, filtration, settled method), in the solution mono-glycerides that has concentrated.The scope of service temperature is a room temperature to 100.This method can be isolated high dense mono-glycerides product from thick ester, but its deficiency is also arranged.As: (1) solvent is expensive; (2) cold analysis temperature is low.The patent report is minimum to be room temperature, but because ketone has solvability preferably to the ester class, in fact cold analysis temperature is about-20 ℃.(3) ketones solvent is favourable to the neutralized reaction product (being generally sodium phosphate or potassiumphosphate) of removing glycerine in the thick ester and catalyzer, but effect is not satisfactory, and glycerol content is generally greater than 2.7% in the mono-glycerides product.
380,605 of russian patent SU implement solvent crystallization as chloroform, tetracol phenixin, benzene, hexanaphthene, sherwood oil etc. to the primary products of mono-glycerides with non-polar organic solvent.Basic step also comprises dissolving, cold analysis, filtration and product desolventizing etc.Solvent temperature is 40～70 ℃, and Tc is 19～30 ℃.Can obtain 95～100% mono-glycerides product thus.According to reports, usefulness 70g benzene dissolves 10g mono-glycerides primary products in 60～65 ℃ after, be cooled to 19～20 ℃,, can get 98.2% mono-glycerides product after the drying the solid filtering of separating out.The technology that this patent provided can obtain high-purity mono-glycerides, and weak point is: (1) solvent costliness and partial solvent are poisonous as chloroform, tetracol phenixin etc.This production to main mono-glycerides as food emulsifier is very unfavorable.(2) separate mono-glycerides with non-polar solvent, the cold analysis order is followed successively by glycerine, lipid acid, list, two, Witepsol W-S 55.Therefore, must contain more glycerine and lipid acid in the product of flow process that patent is described, promptly its technology is to removing glycerine and lipid acid is unfavorable.
Above-mentioned patent or reported in literature about solvent crystallization separation mono-glycerides respectively have its suitability.But weak point is arranged all.Ubiquitous problem is: 1) solvent costliness; 2) solvent for use is difficult to remove glycerine and the lipid acid in the product; 3), all not complete technology from the angle of industrial application.
The objective of the invention is to develop an industrialized mono-glycerides separating technology of energy, so that isolate content greater than 90% mono-glycerides product from the mono-glycerides primary products that contain mono-glycerides 40～60%, and the yield that makes mono-glycerides in the product is greater than 90%.
The present invention is a kind of technology with separating mono fatty acid glyceride by solvent crystallizing method, it is characterized in that the primary products of dissolving monoglyceride with solvent under 55 ℃～62 ℃ stirrings; Gained solution is cooled to 30 ℃～46 ℃, separates out most of dialycerides fat acid esters and fatty acid triglyceride; Filter out and separate out solid and it is being lower than 150 ℃ of dryings down; Filtrate is cooled to 15 ℃～26 ℃ again, separates out monoglyceride; Filter out the monoglyceride solid of separating out and with its be lower than 150 ℃ dry down; It is multiplexing that filtrate turns back to dissolution process; 1～3 time multiplexing back steams solvent with distillation method, impurity such as deglycerizin; Solvent for use is that the carbon atom quantity of one or two or more kinds is 1～6 saturated fatty alcohol (comprising that it is corresponding with a part isomer).Ethanol is best.Solvent is preferably the mixture of this saturated fatty alcohol and water, and for methyl alcohol, ethanol and propyl alcohol, the concentration of water is preferably 1～25% in the miscellany; Concentration for water in other saturated alcohol (butanols, amylalcohol and hexanol) mixture is preferably 1～15%.
The mass ratio of solvent and solute is preferably 0.5～6 in the dissolving.
Describe the present invention below in conjunction with accompanying drawing.
Process flow sheet of the present invention is seen shown in the accompanying drawing.Each unit is respectively among the figure: 1. dissolving; 2. cold analysis; 3. filter; 4. cold analysis; 5. filter; 6.7. it is dry.
1. dissolving: take the mass ratio of solvent and the solute ratio as 0.5～6, solvent, solute (thick ester) is mixed after, in situation about stirring, be heated to 55～62 ℃, make it to be dissolved as fully uniform solution. Wherein the mass ratio of solvent, solute should be chosen according to the difference of the monoglyceride primary product of processing and the difference of institute's solvent-applied. , monoglyceride carbon atom quantity more high such as content of monoglyceride in the thick ester more less, the solvent alcohol carbon atom quantity is more many, and then solvent solute mass ratio is just more big.
2. cold analysis:
With cooling medium (such as cooling-air, cooling water) solution of 1 gained is cooled to 30～46 ℃, then there is solid to separate out, because molecular weight and the polarity order of each component are followed successively by glycerine, aliphatic acid, monoglyceride, two sweet esters, triglyceride in the monoglyceride primary product, the solid of separating out earlier thus, is followed successively by triglyceride, two sweet esters. By control cold analysis temperature, most triglyceride, two sweet esters are separated out and only have a small amount of monoglyceride Separate out, thereby reach the purpose of from thick ester, removing triglyceride, two sweet esters.
The selection of cold analysis temperature should recently be determined according to kind, content and solvent, the solute of monoglyceride in the thick ester. As: big, the solvent of carbon atom quantity, solute then should be selected higher cold analysis temperature than little in content of monoglyceride height, the monoglyceride.
3. filter: implement liquid one solid separation.Can select multiple mode for use, as vacuum filtration, press filtration and centrifugation etc.
4. cold analysis: operation is with 2, and the cold analysis temperature is lower, between 15～26 ℃.This temperature choose with raw material in mono-glycerides kind, content and the product concentration, the yield of mono-glycerides relevant.This temperature controlling should make mono-glycerides separate out as far as possible, and glycerine, lipid acid are then stayed in the solution.
5. filter: operation is with 3.Filtrate filtered L
2, can turn back to the 1.(dissolving) and middle the use, after reusing 1～3 time, steam solvent to remove the neutralized reaction product of the glycerine, lipid acid, a small amount of mono-glycerides and the catalyzer that are dissolved in wherein with the method for distilling (comprising vacuum distilling).The number of times that recycles depends on glycerol content in the thick ester.The foundation that number of times is reused in decision is that the glycerol content in the product mono-glycerides is limited in below the required value.
6. dry: as can to select for use any service temperature to be lower than 150 ℃ method to the drying of mono-glycerides finished product, in order to avoid cause the thermolysis or the thermally denature of mono-glycerides.The drying effect that dusts is best, and one can reclaim the solvent of carrying secretly in the solid precipitate, its two, can make the product powdered.
7. dry: purpose is to reclaim the solvent of carrying secretly in the solid precipitate.Can select for use any service temperature to be lower than 150 ℃ drying means.Dried solid, its main component are two sweet esters, also have a small amount of triglyceride and mono-glycerides.Can in mono-glycerides synthetic, use, carry out glycerolysis reaction to prepare mono-glycerides.
Wherein, 6,7 collected solution L can directly use in 1.
Use specified solvent and the technology of the present invention, can from the primary products that contain mono-glycerides 40～60%, isolate the mono-glycerides product more than 90%, and can make in the product glycerol content less than 1.2%, fatty acid content is less than 1.5%, and do not contain the neutralized reaction product of catalyzer in the product substantially.In other words, use this technology, only can realize removing glycerine, lipid acid and catalyzer neutralized reaction product in the thick ester with a kind of solvent (can be double solvents), make simultaneously that the content of mono-glycerides reaches 90% the above object in the product, the yield of mono-glycerides is also above 90% in the product.
From composition, comprise low carbon fat alcohol (C1-C6) in the solvent, be the stronger solvent of polarity.Under warm condition,, good solvability is arranged, and along with the reduction of temperature as mono-glycerides, two sweet esters, triglyceride to glyceryl ester, widely different to the solubility change of the glyceryl ester of the hydroxyl that contains different numbers.If in alcohol, add an amount of water, polarity of solvent is changed, more help the separation of glyceryl ester.And, because the unlimited compatibility of G ﹠ W, make easier being removed of glycerine in the mono-glycerides primary products; Simultaneously, the existence of water is more conducive to remove catalyzer neutralized reaction product wherein, as sodium phosphate or potassiumphosphate.And alcohol makes lipid acid also can be removed to ester fat acid good solubility.This shows, utilize the double solvents of low-carbon (LC) alcohol and water that the primary products of mono-glycerides are implemented Crystallization Separation, can obtain good separating effect.This technical process is simple, pollution-free, be easy to industrialization.
The available chemical method of the analysis of mono-glycerides, i.e. iodimetry,iodometry.Its principle is with Periodic acid (HIO
4Or HIO
42H
2O) come the oxidation vicinal hydroxyl groups, then generate iodine with the excessive Periodic acid of potassiumiodide reduction.The iodine of separating out again with the sodium thiosulfate standard solution titration, thus content of monoglyceride measured.This method can only be measured α-Dan Ganzhi content, but β-mono-glycerides accounts for 5～8% of total content of monoglyceride, can estimate the content of total mono-glycerides thus.
The mensuration of total content of monoglyceride is generally used chromatography (gas phase or liquid phase).Its principle is to utilize the difference of each component molecular weight in the mono-glycerides mixture, in chromatographic column, separates, thus metering.
Experimentize according to front technology, it is as follows to obtain embodiment:
Claims (6)
1, a kind of technology with separating mono fatty acid glyceride by solvent crystallizing method is characterized in that the primary products of dissolving monoglyceride with solvent under 55 ℃～62 ℃ stirrings; Gained solution is cooled to 30 ℃～46 ℃, separates out most of dialycerides fat acid esters and fatty acid triglyceride; Filter out and separate out solid and it is being lower than 150 ℃ of dryings down; Filtrate then is cooled to 15 ℃～26 ℃, separates out monoglyceride; Filter out the monoglyceride solid of separating out and it is being lower than 150 ℃ of dryings; It is multiplexing that filtrate turns back to dissolution process; 1～3 time multiplexing back steams solvent with distillation method, impurity such as deglycerizin; Solvent for use is that the carbon atom quantity of one or two or more kinds is 1～6 saturated fatty alcohol (comprising that it is corresponding with a part isomer).
2, according to the said technology of claim 1, it is characterized in that said solvent is an ethanol with separating mono fatty acid glyceride by solvent crystallizing method.
3, according to the said technology of claim 1, it is characterized in that the miscellany of said solvent for this saturated fatty alcohol and water with separating mono fatty acid glyceride by solvent crystallizing method.
4, according to the said technology with separating mono fatty acid glyceride by solvent crystallizing method of claim 3, it is characterized in that said solvent is a kind of in methyl alcohol, ethanol and the propyl alcohol, the concentration of water is preferably 1～25% in the miscellany.
5, according to the said technology with separating mono fatty acid glyceride by solvent crystallizing method of claim 3, it is characterized in that said solvent is a kind of in butanols, amylalcohol and the hexanol, the concentration of water is preferably 1～15% in the miscellany.
6, according to claim 1,2,3,4 and 5 said technologies, it is characterized in that in the said dissolving that the mass ratio of solvent and solute is 0.5～6 with separating mono fatty acid glyceride by solvent crystallizing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92100594 CN1030072C (en) | 1992-01-31 | 1992-01-31 | Process for separating mono fatty acid glyceride by solvent crystallizing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92100594 CN1030072C (en) | 1992-01-31 | 1992-01-31 | Process for separating mono fatty acid glyceride by solvent crystallizing method |
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| CN1074898A true CN1074898A (en) | 1993-08-04 |
| CN1030072C CN1030072C (en) | 1995-10-18 |
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| CN 92100594 Expired - Fee Related CN1030072C (en) | 1992-01-31 | 1992-01-31 | Process for separating mono fatty acid glyceride by solvent crystallizing method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345951C (en) * | 2000-07-13 | 2007-10-31 | 花王株式会社 | Solid-liquid separation method of oil composition |
| CN104073364A (en) * | 2014-07-22 | 2014-10-01 | 中南林业科技大学 | Technology for preparing lauric acid by adopting litsea cubeba kernel oil |
| CN114920642A (en) * | 2022-06-02 | 2022-08-19 | 浙江工业大学 | Separation process for obtaining high-purity fatty acid monoglyceride and fatty acid diglyceride |
| CN115418380A (en) * | 2022-09-29 | 2022-12-02 | 暨南大学 | Purification method of diglyceride |
-
1992
- 1992-01-31 CN CN 92100594 patent/CN1030072C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345951C (en) * | 2000-07-13 | 2007-10-31 | 花王株式会社 | Solid-liquid separation method of oil composition |
| CN104073364A (en) * | 2014-07-22 | 2014-10-01 | 中南林业科技大学 | Technology for preparing lauric acid by adopting litsea cubeba kernel oil |
| CN114920642A (en) * | 2022-06-02 | 2022-08-19 | 浙江工业大学 | Separation process for obtaining high-purity fatty acid monoglyceride and fatty acid diglyceride |
| CN114920642B (en) * | 2022-06-02 | 2024-03-12 | 浙江工业大学 | Separation process for obtaining high-purity fatty acid monoglyceride and fatty acid diglyceride |
| CN115418380A (en) * | 2022-09-29 | 2022-12-02 | 暨南大学 | Purification method of diglyceride |
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| Publication number | Publication date |
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| CN1030072C (en) | 1995-10-18 |
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