CN101486954B - Method for separating oleate, trans-oleate and trans-oleate - Google Patents
Method for separating oleate, trans-oleate and trans-oleate Download PDFInfo
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- CN101486954B CN101486954B CN2009100737765A CN200910073776A CN101486954B CN 101486954 B CN101486954 B CN 101486954B CN 2009100737765 A CN2009100737765 A CN 2009100737765A CN 200910073776 A CN200910073776 A CN 200910073776A CN 101486954 B CN101486954 B CN 101486954B
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Abstract
The invention discloses a separating method of oleic acid and trans-form oleic acid, and oleate and trans-form oleate, which uses silica gel, active carbon or alumina as a carrier, dissolves the urea, the quality ratio of which and the carrier being 1: 0.1 to 10, by solvent and infuses the urea on the carrier; the loading-type urea obtained by removing the solvent serves as fixed phase and loaded into the chromatographic column; the mixture raw materials to be separated, containing oleic acid and trans-form oleic acid or oleate and trans-form oleate, are added into the upper column; elution is carried out by mobile phase, and the elution portions in different periods are collected; and through gas chromatography detection, the solvent is removed from the collected elution portions rich in oleic acid and trans-form oleic acid or oleate and trans-form oleate to obtain high-purity oleic acid and trans-form oleic acid products or oleate and trans-form oleate products. The method has the advantages of simple and effective separation, high purity of the obtained product, and low operation cost.
Description
Affiliated field
The invention belongs to field of grease chemical technology, relate in particular to the separation method of a kind of oleic acid and antiform oleic acid or oleic acid ester and vaccenic acid esters.
Background technology
High purity oleic acid is applicable to fields such as medicine, cosmetic, information technology, bio-science research, biotechnology, have effects such as unique hypoglycemic, regulating blood fat, decreasing cholesterol, can be used as medicine intermediate and use, high purity oleic acid product also is applicable to the industry use that senior clean-out system, essence and flavoring agent, senior lubricant additive and metal processing aid etc. are had relatively high expectations.
Oleic acid usually with lipid acid coexistences such as linolic acid, linolenic acid, adopt urea adduct method, low temperature crystallization etc. to carry out the separation of different pair key lipid acid usually.But its chemical structure only differs a carbon-carbon double bond respectively, and physicochemical property are approaching, and the separation efficiency in crystallization and the inclusion process is extremely low, causes separation efficiency and yield existing problems.
The selective reaction method prepares high-purity oleic acid and has proposed a kind of new thinking (application chemical industry 2005,34 (12): 748), linolic acid and linolenic acid are polyunsaturated fatty acid, Hu Sheng etc. generate 22 carbon tricarboxylic anhydrides by the conjugation isomery of catalysis of iodine polyene fatty acid and then with the addition of MALEIC ANHYDRIDE generation diene, separate with unreacted oleic acid by distillation then, can obtain high-purity oleic acid.But in catalysis of iodine conjugated process, there is part oleic acid that isomerization reaction inevitably takes place and generates antiform oleic acid, though the content of antiform oleic acid reduces along with the reduction of catalytic amount and temperature of reaction, even when reducing temperature of reaction to 180 ℃, the content of antiform oleic acid still surpasses 10%.And the reduction catalyst content can cause the transformation efficiency of linolic acid conjugation isomery to reduce and do not reach separation oleic acid and linoleic purpose.Can adopt the shortening technology to carry out lipid acid hydrogenation in addition and prepare oleic acid (household chemicals science, 2006,29 (1): 19), making wherein, linolic acid, linolenic acid all are transformed into oleic acid, but in hydrogenation process, oleic acid can spontaneously transform to more stable antiform oleic acid, causes also can producing a large amount of antiform oleic acids in the lipid acid hydrogenation process.Trans fatty acid is taken in when surpassing certain value concentration of low density lipoprotein cholesterol in the rising blood plasma, reduce high density lipoprotein cholesterol concentration, obviously increase and suffer from risk of cardiovascular diseases, trans fatty acid also can disturb indispensable fatty acid eubolism in vivo, also may influence upgrowth and development of children and neural system health.Countries in the world are just taking corresponding measure to reduce content of trans fatty acids in the food.Denmark, the U.S., Canada have begun to enact a law, and the content of trans fatty acid must indicate in Compulsory Feature foodstuff production manufacturer on all nutritional labelings in the food product pack.
At present also there is not effectively to separate the way of oleic acid and antiform oleic acid, oleic acid ester and vaccenic acid esters.
Summary of the invention
The separation method that the purpose of this invention is to provide a kind of oleic acid and antiform oleic acid, oleic acid ester and trans grease.
The present invention is that the mixture with the mixture that contains oleic acid and antiform oleic acid, oleic acid ester and vaccenic acid esters is a raw material, and loading type urea is stationary phase, and column chromatography for separation obtains high purity oleic acid or its methyl esters/ethyl ester product.
Concrete operations step of the present invention is as follows:
(1) selecting silica gel, gac or aluminum oxide for use is carrier, will be that 1: 0.1～10 urea is impregnated on the carrier by dissolution with solvents with the carrier mass ratio, removes loading type urea that solvent obtains as stationary phase, the chromatography column of packing into;
(2) column chromatography: will isolatingly contain the mixture of oleic acid and antiform oleic acid or the mixture material upper prop of oleic acid ester and vaccenic acid esters, and carry out wash-out, and collect the elution fraction of different periods with moving phase;
(3) desolventizing: by gas chromatographic detection,, remove solvent, obtain high-purity oleic acid, antiform oleic acid product or oleic acid ester, vaccenic acid esters product with elution fraction of collecting that is rich in oleic acid, antiform oleic acid or the elution fraction that is rich in oleic acid ester, vaccenic acid esters.
Aforesaid oleic acid ester is oleic methyl esters, ethyl ester, propyl ester or butyl ester, and the vaccenic acid esters is methyl esters, ethyl ester, propyl ester or the butyl ester of antiform oleic acid.
As described in (1) step, solvent for use is the mixing solutions of water-alcoholic solution, alcohol or various alcohol, and described alcohol refers to carbonatoms less than 4 monohydroxy-alcohol, particular methanol, ethanol or Virahol.
As described in (2) step, used moving phase is any dissolves fat acid or the fatty acid ester not solvent or the solution of dissolved urea, or the urea saturated solution of any dissolves fat acid or fatty acid ester.
The solvent of described not dissolved urea be sherwood oil, normal hexane, chloroform, ethyl acetate, methyl acetate one or more,
The solution of described not dissolved urea be urea saturated solution, the ethyl acetate alcoholic solution of urea saturated solution, the alcoholized chloroform solution of urea saturated solution, the normal hexane alcoholic solution of sherwood oil alcoholic solution urea saturated solution, methyl acetate alcoholic solution urea saturated solution one or more.
The urea saturated solution of described dissolves fat acid or fatty acid ester be urea saturated solution, the ethyl acetate alcoholic solution of urea saturated solution, the alcoholized chloroform solution of urea saturated solution, the normal hexane alcoholic solution of methyl alcohol urea saturated solution, ethanol urea saturated solution or sherwood oil alcoholic solution urea saturated solution, methyl acetate alcoholic solution urea saturated solution one or more.
Alcohol in the described alcoholic solution is methyl alcohol or ethanol.
The present invention has following characteristics:
1. the mixture, oleic acid ester of having realized containing oleic acid and antiform oleic acid simply effectively separates products obtained therefrom purity height with the mixture of vaccenic acid esters;
2. running cost is low, environmental protection;
3. technology is simple, is easy to industrialization.
Embodiment
Embodiment 1:
Take by weighing 15g urea, be dissolved in the solution of moisture 25wt% methyl alcohol, add the 30g alumina supporter, decompression rotation evaporate to dryness is produced the stationary phase that load has urea; Separate by molecular distillation after catalysis of iodine cottonseed oil fatty acid conjugation and the addition of MALEIC ANHYDRIDE diene and obtain containing the oleic acid mixture of antiform oleic acid as raw material, with the pipette, extract 2ml raw material column chromatography of packing into, prepare the ethanolic soln that contains sherwood oil 6wt%, carry out wash-out with the saturated back of urea as moving phase, oleic acid and antiform oleic acid content in the gas chromatographic detection elutriant, the elution fraction of oleic acid and antiform oleic acid is rich in collection, merge evaporate to dryness respectively, obtain the oleic acid of content 98wt% and the antiform oleic acid of 96wt%.
Embodiment 2:
Take by weighing 30g urea, be dissolved in the ethanolic soln that contains methyl alcohol 50wt%, be made into saturated solution, add the 25g silica-gel carrier, freezing stirred crystallization is filtered, and produces the stationary phase that load has urea; With sherwood oil as moving phase; The hydrogenation oleic acid that contains the oleic acid mixture of antiform oleic acid with the pipette, extract 5ml column chromatography of packing into, oleic acid and antiform oleic acid content in the gas chromatographic detection elutriant, the elution fraction of oleic acid and antiform oleic acid is rich in collection, merge evaporate to dryness respectively, obtain the oleic acid of content 96wt% and the antiform oleic acid of 95wt%.
Embodiment 3:
Take by weighing 40g urea, be dissolved in the anhydrous methanol, be made into saturated solution, add the 10g silica-gel carrier, slowly add dehydrated alcohol, allow urea slowly separate out, load on the silica gel, filter, produce the stationary phase that load has urea; With normal hexane as moving phase; Separate the oleic acid mixture and the methyl alcohol that obtain containing antiform oleic acid by molecular distillation after catalysis of iodine cottonseed oil fatty acid conjugation and the addition of MALEIC ANHYDRIDE diene and carry out the product of esterification as raw material, with the pipette, extract 6ml column chromatography of packing into, Witconol 2301 and antiform oleic acid methyl esters content in the gas chromatographic detection elutriant, the elution fraction of Witconol 2301 and antiform oleic acid methyl esters is rich in collection, merge evaporate to dryness respectively, obtain the Witconol 2301 of content 99wt% and the antiform oleic acid methyl esters of 98wt%.
Embodiment 4:
Take by weighing 50g urea, be dissolved in the 80wt% Virahol, be made into saturated solution, add the 10g absorbent charcoal carrier, decompression rotation evaporate to dryness allows urea load on the gac, filters, and produces the stationary phase that load has urea; Be made into the ethanolic soln that contains 1wt% methyl alcohol, use the saturated back of urea as moving phase; Separate the oleic acid mixture and the ethanol that obtain containing antiform oleic acid by molecular distillation after catalysis of iodine cottonseed oil fatty acid conjugation and the addition of MALEIC ANHYDRIDE diene and carry out the product of esterification as raw material, with the pipette, extract 5ml column chromatography of packing into, ethyl oleate and antiform oleic acid ethyl ester content in the gas chromatographic detection elutriant, the elution fraction of ethyl oleate and antiform oleic acid ethyl ester is rich in collection, merge evaporate to dryness respectively, obtain the ethyl oleate of content 99wt% and the antiform oleic acid ethyl ester of 96wt%.
Embodiment 5:
Take by weighing 10g urea, be dissolved in the anhydrous methanol, be made into saturated solution, add the 50g alumina supporter, decompression rotation evaporate to dryness is produced the stationary phase that load has urea; With ethyl acetate as moving phase; With the oleic acid mixture of pipette, extract 2ml embodiment 1 column chromatography of packing into, oleic acid and antiform oleic acid content in the gas chromatographic detection elutriant, the elution fraction of oleic acid and antiform oleic acid is rich in collection, merges evaporate to dryness respectively, obtains the oleic acid of content 97wt% and the antiform oleic acid of 98wt%.
Embodiment 6:
Take by weighing 30g urea, in the solution 95wt% methyl alcohol, be made into saturated solution, add the 50g absorbent charcoal carrier, decompression rotation evaporate to dryness is produced the stationary phase that load has urea; Be made into the alcohol saturated solution of urea, as moving phase; The product that carries out esterification with oleic acid mixture and the propyl alcohol of pipette, extract 2ml embodiment 1 column chromatography of packing into, oleic acid propyl ester and antiform oleic acid propyl ester content in the gas chromatographic detection elutriant, the elution fraction of oleic acid propyl ester and antiform oleic acid propyl ester is rich in collection, merge evaporate to dryness respectively, obtain the oleic acid propyl ester of content 95wt% and the antiform oleic acid propyl ester of 96wt%.
Embodiment 7:
Take by weighing 15g urea, be dissolved in the solution of moisture 35wt% methyl alcohol, add the 30g alumina supporter, decompression rotation evaporate to dryness is produced the stationary phase that load has urea; Separate by molecular distillation after catalysis of iodine cottonseed oil fatty acid conjugation and the addition of MALEIC ANHYDRIDE diene and obtain containing the oleic acid mixture of antiform oleic acid as raw material, with the pipette, extract 2ml raw material column chromatography of packing into, prepare the ethanolic soln that contains ethyl acetate 6wt%, carry out wash-out with the saturated back of urea as moving phase, oleic acid and antiform oleic acid content in the gas chromatographic detection elutriant, the elution fraction of oleic acid and antiform oleic acid is rich in collection, merge evaporate to dryness respectively, obtain the oleic acid of content 98wt% and the antiform oleic acid of 96wt%.
Embodiment 8:
Take by weighing 30g urea, be dissolved in the ethanolic soln that contains methyl alcohol 60wt%, be made into saturated solution, add the 25g silica-gel carrier, freezing stirred crystallization is filtered, and produces the stationary phase that load has urea; With chloroform as moving phase; With the hydrogenation oleic acid of pipette, extract 5ml embodiment 2 column chromatography of packing into, oleic acid and antiform oleic acid content in the gas chromatographic detection elutriant, the elution fraction of oleic acid and antiform oleic acid is rich in collection, merges evaporate to dryness respectively, obtains the oleic acid of content 95wt% and the antiform oleic acid of 93wt%.
Embodiment 9:
Take by weighing 40g urea, be dissolved in the anhydrous methanol, be made into saturated solution, add the 10g silica-gel carrier, slowly add dehydrated alcohol, allow urea slowly separate out, load on the silica gel, filter, produce the stationary phase that load has urea; With methyl acetate as moving phase; The product that carries out esterification with pipette, extract 6ml embodiment 1 oleic acid mixture and the butanols column chromatography of packing into, butyl oleate and antiform oleic acid butyl ester content in the gas chromatographic detection elutriant, the elution fraction of butyl oleate and antiform oleic acid butyl ester is rich in collection, merge evaporate to dryness respectively, obtain the butyl oleate of content 98wt% and the antiform oleic acid butyl ester of 99wt%.
Embodiment 10:
Take by weighing 50g urea, be dissolved in the 80wt% Virahol, be made into saturated solution, add the 10g absorbent charcoal carrier, decompression rotation evaporate to dryness allows urea load on the gac, filters, and produces the stationary phase that load has urea; Be made into the ethyl acetate solution that contains 3wt% methyl alcohol, use the saturated back of urea as moving phase; The product that carries out esterification with pipette, extract 5ml embodiment 1 oleic acid mixture and the ethanol column chromatography of packing into, ethyl oleate and antiform oleic acid ethyl ester content in the gas chromatographic detection elutriant, the elution fraction of ethyl oleate and antiform oleic acid ethyl ester is rich in collection, merge evaporate to dryness respectively, obtain the ethyl oleate of content 96wt% and the antiform oleic acid ethyl ester of 98wt%.
Embodiment 11:
Take by weighing 10g urea, be dissolved in the anhydrous methanol, be made into saturated solution, add the 50g alumina supporter, decompression rotation evaporate to dryness is produced the stationary phase that load has urea; With volume ratio is that 1: 1 chloroform and normal hexane mixed solution are as moving phase; With the oleic acid mixture of pipette, extract 2ml embodiment 1 column chromatography of packing into, oleic acid and antiform oleic acid content in the gas chromatographic detection elutriant, the elution fraction of oleic acid and antiform oleic acid is rich in collection, merges evaporate to dryness respectively, obtains the oleic acid of content 99wt% and the antiform oleic acid of 98wt%.
Embodiment 12:
Take by weighing 30g urea, in the solution 95wt% methyl alcohol, be made into saturated solution, add the 50g absorbent charcoal carrier, decompression rotation evaporate to dryness is produced the stationary phase that load has urea; Be made into volume ratio and be 10: 1 normal hexane and alcohol mixeding liquid, add urea and fully dissolve, be made into the saturated solution of urea, as moving phase; Mix the product that carries out esterification with the methyl alcohol column chromatography of packing into the oleic acid of pipette, extract 2ml embodiment 1, Witconol 2301 and antiform oleic acid methyl esters content in the gas chromatographic detection elutriant, the elution fraction of Witconol 2301 and antiform oleic acid methyl esters is rich in collection, merge evaporate to dryness respectively, obtain the Witconol 2301 of content 98wt% and the antiform oleic acid methyl esters of 97wt%.
Claims (7)
1. the separation method of an oleic acid and antiform oleic acid, oleic acid ester and vaccenic acid esters is characterized in that comprising the steps:
(1) being carrier with silica gel, gac or aluminum oxide, will be that 1: 0.1～10 urea is impregnated on the carrier by dissolution with solvents with the carrier mass ratio, remove loading type urea that solvent obtains as stationary phase, the chromatography column of packing into;
(2) column chromatography: will isolatingly contain the mixture of oleic acid and antiform oleic acid or the mixture material upper prop of oleic acid ester and vaccenic acid esters, and carry out wash-out, and collect the elution fraction of different periods with moving phase;
(3) desolventizing: by gas chromatographic detection,, remove solvent, obtain high-purity oleic acid, antiform oleic acid product or oleic acid ester, vaccenic acid esters product with elution fraction of collecting that is rich in oleic acid, antiform oleic acid or the elution fraction that is rich in oleic acid ester, vaccenic acid esters;
Described moving phase be urea saturated solution, the ethyl acetate alcoholic solution of urea saturated solution, the alcoholized chloroform solution of urea saturated solution, the normal hexane alcoholic solution of sherwood oil alcoholic solution urea saturated solution, methyl acetate alcoholic solution urea saturated solution one or more.
2. the separation method of a kind of according to claim 1 oleic acid and antiform oleic acid, oleic acid ester and vaccenic acid esters is characterized in that described oleic acid ester is oleic methyl esters, ethyl ester, propyl ester or butyl ester.
3. the separation method of a kind of according to claim 1 oleic acid and antiform oleic acid, oleic acid ester and vaccenic acid esters is characterized in that described vaccenic acid esters is the methyl esters of antiform oleic acid, ethyl ester, propyl ester or butyl ester.
4. the separation method of a kind of according to claim 1 oleic acid and antiform oleic acid, oleic acid ester and vaccenic acid esters is characterized in that described step (1) solvent for use is water-alcohol solution, alcohol or pure mixing solutions.
5. as the separation method of a kind of oleic acid as described in the claim 4 and antiform oleic acid, oleic acid ester and vaccenic acid esters, it is characterized in that described alcohol is carbonatoms less than 4 monohydroxy-alcohol.
6. as the separation method of a kind of oleic acid as described in the claim 5 and antiform oleic acid, oleic acid ester and vaccenic acid esters, it is characterized in that described carbonatoms is methyl alcohol, ethanol or Virahol less than 4 monohydroxy-alcohol.
7. the separation method of a kind of according to claim 1 oleic acid and antiform oleic acid, oleic acid ester and vaccenic acid esters is characterized in that the alcohol in the described moving phase alcoholic solution is methyl alcohol or ethanol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100737765A CN101486954B (en) | 2009-02-11 | 2009-02-11 | Method for separating oleate, trans-oleate and trans-oleate |
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| CN2009100737765A CN101486954B (en) | 2009-02-11 | 2009-02-11 | Method for separating oleate, trans-oleate and trans-oleate |
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| CN101486954B true CN101486954B (en) | 2011-06-22 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101838589A (en) * | 2010-05-25 | 2010-09-22 | 九江力山环保科技有限公司 | Production process of low-antiform oleic acid |
| CN102921192B (en) * | 2012-05-16 | 2014-11-12 | 中国计量科学研究院 | Method for preparing high purity monounsaturated fatty acid |
| CN105419949B (en) * | 2015-11-04 | 2020-01-07 | 江南大学 | Method for micro-separation and enrichment of branched chain fatty acid |
| CN106496021A (en) * | 2016-10-24 | 2017-03-15 | 烟台燕园科玛健康产业有限公司 | A kind of high-purity alpha linolenic acid separating technology |
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