CN101016242A - Method of preparing linolenic acid and linolenic acid lower member ester by urea column chromatography - Google Patents
Method of preparing linolenic acid and linolenic acid lower member ester by urea column chromatography Download PDFInfo
- Publication number
- CN101016242A CN101016242A CN 200710061440 CN200710061440A CN101016242A CN 101016242 A CN101016242 A CN 101016242A CN 200710061440 CN200710061440 CN 200710061440 CN 200710061440 A CN200710061440 A CN 200710061440A CN 101016242 A CN101016242 A CN 101016242A
- Authority
- CN
- China
- Prior art keywords
- linolenic acid
- urea
- column chromatography
- oil
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 title claims abstract description 91
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 235000020661 alpha-linolenic acid Nutrition 0.000 title claims abstract description 76
- 229960004488 linolenic acid Drugs 0.000 title claims abstract description 76
- 239000004202 carbamide Substances 0.000 title claims abstract description 68
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000004440 column chromatography Methods 0.000 title claims abstract description 35
- 150000002148 esters Chemical class 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 17
- -1 ester fatty acid ester Chemical class 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 13
- 229930195729 fatty acid Natural products 0.000 claims abstract description 13
- 239000000194 fatty acid Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 7
- 238000010828 elution Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 75
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000003921 oil Substances 0.000 claims description 26
- 235000019198 oils Nutrition 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 239000012047 saturated solution Substances 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 244000298697 Actinidia deliciosa Species 0.000 claims description 6
- 235000009436 Actinidia deliciosa Nutrition 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 235000004347 Perilla Nutrition 0.000 claims description 6
- 244000124853 Perilla frutescens Species 0.000 claims description 6
- 229940094199 black currant oil Drugs 0.000 claims description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 238000006136 alcoholysis reaction Methods 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 claims description 4
- 235000009434 Actinidia chinensis Nutrition 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229940089020 evening primrose oil Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 240000000950 Hippophae rhamnoides Species 0.000 claims 2
- 235000003145 Hippophae rhamnoides Nutrition 0.000 claims 2
- 241000219925 Oenothera Species 0.000 claims 2
- 235000004496 Oenothera biennis Nutrition 0.000 claims 2
- 235000021388 linseed oil Nutrition 0.000 claims 2
- 239000000944 linseed oil Substances 0.000 claims 2
- 229940060184 oil ingredients Drugs 0.000 claims 2
- 150000003672 ureas Chemical class 0.000 claims 2
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 claims 1
- 235000007650 Aralia spinosa Nutrition 0.000 claims 1
- 235000002566 Capsicum Nutrition 0.000 claims 1
- 239000006002 Pepper Substances 0.000 claims 1
- 235000016761 Piper aduncum Nutrition 0.000 claims 1
- 235000017804 Piper guineense Nutrition 0.000 claims 1
- 244000203593 Piper nigrum Species 0.000 claims 1
- 235000008184 Piper nigrum Nutrition 0.000 claims 1
- 241000949456 Zanthoxylum Species 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 238000012856 packing Methods 0.000 claims 1
- 241000894007 species Species 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 14
- 229940090028 ethyl linolenate Drugs 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 229960004756 ethanol Drugs 0.000 description 9
- 235000020664 gamma-linolenic acid Nutrition 0.000 description 9
- 150000002632 lipids Chemical class 0.000 description 9
- 230000001476 alcoholic effect Effects 0.000 description 8
- VZCCETWTMQHEPK-QNEBEIHSSA-N gamma-linolenic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/CCCCC(O)=O VZCCETWTMQHEPK-QNEBEIHSSA-N 0.000 description 8
- VZCCETWTMQHEPK-UHFFFAOYSA-N gamma-Linolensaeure Natural products CCCCCC=CCC=CCC=CCCCCC(O)=O VZCCETWTMQHEPK-UHFFFAOYSA-N 0.000 description 7
- 229960002733 gamolenic acid Drugs 0.000 description 7
- 244000196929 Oenothera glazioviana Species 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- 235000013305 food Nutrition 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 238000000199 molecular distillation Methods 0.000 description 5
- 235000003935 Hippophae Nutrition 0.000 description 4
- 241000229143 Hippophae Species 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- 241000008871 Microula Species 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 230000003110 anti-inflammatory effect Effects 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- DVSZKTAMJJTWFG-UHFFFAOYSA-N docosa-2,4,6,8,10,12-hexaenoic acid Chemical compound CCCCCCCCCC=CC=CC=CC=CC=CC=CC(O)=O DVSZKTAMJJTWFG-UHFFFAOYSA-N 0.000 description 2
- MBMBGCFOFBJSGT-KUBAVDMBSA-N docosahexaenoic acid Natural products CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000020673 eicosapentaenoic acid Nutrition 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002207 metabolite Substances 0.000 description 2
- DVWSXZIHSUZZKJ-YSTUJMKBSA-N methyl linolenate Chemical class CC\C=C/C\C=C/C\C=C/CCCCCCCC(=O)OC DVWSXZIHSUZZKJ-YSTUJMKBSA-N 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- 230000035764 nutrition Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 150000003180 prostaglandins Chemical class 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 206010012289 Dementia Diseases 0.000 description 1
- 206010012438 Dermatitis atopic Diseases 0.000 description 1
- 208000002249 Diabetes Complications Diseases 0.000 description 1
- 206010012655 Diabetic complications Diseases 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 108090001030 Lipoproteins Proteins 0.000 description 1
- 102000004895 Lipoproteins Human genes 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000036436 anti-hiv Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 201000008937 atopic dermatitis Diseases 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- JYYFMIOPGOFNPK-AGRJPVHOSA-N ethyl linolenate Chemical compound CCOC(=O)CCCCCCC\C=C/C\C=C/C\C=C/CC JYYFMIOPGOFNPK-AGRJPVHOSA-N 0.000 description 1
- JYYFMIOPGOFNPK-UHFFFAOYSA-N ethyl linolenate Natural products CCOC(=O)CCCCCCCC=CCC=CCC=CCC JYYFMIOPGOFNPK-UHFFFAOYSA-N 0.000 description 1
- 235000008524 evening primrose extract Nutrition 0.000 description 1
- 239000010475 evening primrose oil Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003053 immunization Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 150000002617 leukotrienes Chemical class 0.000 description 1
- 230000037356 lipid metabolism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- YEYZNBKNDWPFSQ-UHFFFAOYSA-N methanol;urea Chemical compound OC.NC(N)=O YEYZNBKNDWPFSQ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 125000005480 straight-chain fatty acid group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种尿素柱层析生产亚麻酸和亚麻酸低级酯的方法是将固定相为纯尿素或用溶剂将尿素负载于载体上，装在层析柱里，含有亚麻酸的脂肪酸原料或含有亚麻酸低级酯脂肪酸酯原料上柱，流动相注入层析柱进行洗脱，将收集到的富含亚麻酸或亚麻酸低级酯的洗脱份蒸干，得到高纯产品。本发明具有工艺简单，生产成本低，分离效果好，收率高，绿色环保的优点。A method for producing linolenic acid and lower esters of linolenic acid by urea column chromatography is that the stationary phase is pure urea or the urea is loaded on a carrier with a solvent, and the urea is loaded on a chromatographic column, and the fatty acid raw material containing linolenic acid or containing linolenic acid The lower ester fatty acid ester raw material is put on the column, the mobile phase is injected into the chromatographic column for elution, and the collected eluate rich in linolenic acid or lower linolenic acid ester is evaporated to dryness to obtain a high-purity product. The invention has the advantages of simple process, low production cost, good separation effect, high yield and environmental protection.
Description
Technical field
The present invention relates to the production method of a kind of linolenic acid or linolenic acid lower member ester.
Background of invention
Linolenic acid can be divided into two kinds of alpha-linolenic acid and gamma-linolenic acids, and they are ten eight carbon atom, three pairs of key straight chain fatty acids, and relative molecular weight is 278.
The chemistry of alpha-linolenic acid (Alpha-Linolenie Acid) is called all-cis formula-9,12, and the 15-punicic acid (Allcis-9,12,15-Oc-tadecatrienoicacid).Alpha-linolenic acid can directly carry out katabolism in vivo, and meta-bolites wherein the most important thing is DHA (docosahexenoic acid) and EPA polyunsaturated fatty acid and PG (prostaglandin(PG)) such as (timnodonic acids) as human body cell film composition.A large amount of fundamental researchs, epidemiology survey, animal experiment and clinical observation show: alpha-linolenic acid has reducing cholesterol content, suppresses irritated, anti-inflammatory; vision protection improves intelligence, and is anti-ageing; effects such as reducing blood-fat are approved by international medical community, nutrition educational circles.In view of alpha-linolenic acid has important physiologically active and human body generally lacks present situation, Food and Argriculture OrganizationFAO announced it as essential composition in the human foods in 1978, and decision was worldwide special again in 1993 promotes.Since the nineties in 20th century, many national legislation regulations such as the U.S. must be added alpha-linolenic acid in assigned food and metabolite can be sold.In April, 2002, hold in China Shanghai in " the healthy international symposium of indispensable fatty acid and human nutrition ", the World Health Organization announces that 21 century threatens human life " four big killers "---cardiovascular and cerebrovascular disease, cancer, diabetes, dementia.And alpha-linolenic acid has remarkable effect to control " four big killers ", so be decided to be " 21 century green nourishing protective foods " by meeting.
Gamma-linolenic acid (γ-Linolenie acid, GLA.18:3 Δ
6,9,12N-6) being the unsaturated fatty acids of needed by human, is the structured material of each tissue biological's film, also is the precursor of physiologically active substances such as prostaglandin(PG), leukotriene, arachidonic acid.Studies show that that gamma-linolenic acid has is antibiotic, anti-inflammatory, anti-HIV are infected, antitumor, reducing blood-fat and improve effect such as diabetic complication.China was applied to clinical with the Capsulae Radix Oenotherae erythrosepalae form at first in the world as blood lipid-lowering medicine in 1986, Britain's approval evening primrose oil capsule was used for atopic eczema in 1988, nineteen ninety is ratified gamma-linolenic acid again and is described as the leading role of functional foodstuff " 21 century ", life-time service can be corrected disorders of lipid metabolism, plays effects such as body-building, diseases prevention, anti-ageing, enhancing body immunizing power.As medicine of high-grade nutrient oil, foodstuff additive, makeup and treatment disease etc., its DEVELOPMENT PROSPECT is very wide.
Linolenic acid lower member ester has identical physiological function with linolenic acid, and more stable than linolenic acid.The occurring in nature linolenic acid often is present in the Vegetable oil lipoprotein with multiple lipid acid with the form of glyceryl ester jointly, mainly be present in oleum lini, perilla oil, Oleum Hippophae, microula oil, Chinese gooseberry seed oil or the Fructus Zanthoxyli oil as alpha-linolenic acid, gamma-linolenic acid mainly is present in root of Redsepal Eveningprimrose and the blackcurrant oil, the linolenic acid of these forms is unfavorable for the absorption of human body utilization, so, grease need be reacted into the form of the form, particularly ethyl ester of lipid acid or lipid acid lower member ester; But because the structure of various lipid acid or lipid acid lower member ester is close, similar performance brings difficulty for the separation and the purification of linolenic acid and ester thereof.
Domestic and international linolenic isolation technique all concentrates on methods such as molecular distillation, urea clathration, overcritical separation, membrane sepn, silver or cupric ion complexing at present.Patent of invention CN 1414080A utilizes membrane separation technique four times, obtains the enriched substance of lipid acid, obtains product through molecular distillation then; Patent of invention CN 1837179A and CN 1837182A urea adduct method obtain purity respectively greater than 80% alpha-linolenic acid and ethyl linolenate through freezing, press filtration, extraction and molecular distillation then; Patent of invention CN 1181205C and CN 1189567C utilize supercritical methanol technology to carry out Reaction Separation one step and finish and make purer alpha-linolenic acid and Alpha-ethyl linolenate; Patent of invention CN 1053010C and CN 1394944A utilize urea adduct method to make alpha-linolenic acid and Alpha-ethyl linolenate respectively; Patent of invention CN 1095824C utilizes urea adduct method to obtain alpha-linolenic acid more than 90%, then through methods such as over-churning, column chromatography, molecular distillations, obtains purity greater than 95% Alpha-ethyl linolenate; Patent of invention CN 1344706A utilizes the silver ion complexation column chromatography, obtains high-purity Alpha-ethyl linolenate; Patent of invention CN 1219744C utilizes overcritical isolation technique and overcritical silver ion complexation column chromatography for separation to obtain high-purity Alpha-ethyl linolenate; Patent of invention CN 1651396A utilizes cuprous ion complexing column chromatography technology to separate to obtain content greater than 90% Alpha-ethyl linolenate.Separation about gamma-linolenic acid and lower member ester thereof is detected among the patent of invention CN1253426C, utilizes supercritical extraction, recrystallization, urea and fractional distillation method, obtains product.In the above method, molecular distillation and membrane separation technique often need to cooperate other technology as separation means, and be little in batches, conditional request strictness, cost height; Urea adduct method needs a large amount of urea and methyl alcohol, and separating effect is limited, and yield is very low; The complexing of metal ion isolation technique, because complexing action, complexing agent is difficult to carry out recycling, and give in the oil and fat product and introduce heavy metal ion, can cause serious harm to human body, thoroughly removing these heavy metal ion, make product can reach food rank even other standard of pharmaceutical grade, is a challenge greatly for this technology.
Summary of the invention
The purpose of this invention is to provide that cost is low, yield is high, the production method of free of contamination a kind of linolenic acid or linolenic acid lower member ester environmental protection.
The present invention is to be raw material with the fatty acid ester that contains linolenic lipid acid or contain linolenic acid lower member ester, and urea or urea load carrier are stationary phase, and column chromatography for separation obtains linolenic acid or linolenic acid lower member ester product.
The various fatty acid structures of fat hydrolysis are close, and similar performance separates purification difficult; The various fatty acid ester structures of grease alcoholysis are close, and similar performance separates purification difficult.Utilize carrier that urea or load have urea as stationary phase,, can well separate various lipid acid or lower member ester class as long as select suitable moving phase.This method has that technology is simple, purity is high, yield is high, cost is low, pollute less, be easy to characteristics such as industrialization.
Concrete operations step of the present invention is as follows:
(1) dress post: stationary phase is pure urea or with solvent urea is carried on the carrier, is contained in the chromatography column.
(2) join moving phase: prepare moving phase.
(3) column chromatography: will isolatingly contain linolenic raw material of fatty acid or contain linolenic acid lower member ester fatty acid ester raw material upper prop, moving phase is injected chromatography column and is carried out wash-out, collects the elution fraction of different periods.
(4) evaporate to dryness: the elution fraction evaporate to dryness that is rich in linolenic acid or linolenic acid lower member ester that will collect obtains high purity product.
As described in (1) step, solvent for use is the mixed solution of water-alcohol solution, alcohol or various alcohol,, described alcohol refers to carbonatoms less than 4 monohydroxy-alcohol, particular methanol, ethanol and Virahol.
As described in (1) step, used carrier is gac, aluminum oxide, silica gel etc.
As described in (1) step, the mass ratio of carrier and urea is 10～0.1: 1.
As described in (2) step, used moving phase is the not solvent or the solution of dissolved urea of any solubilized raw material, or the urea saturated solution of any solubilized raw material.The preferred sherwood oil of moving phase, normal hexane, chloroform, ethyl acetate, methyl acetate one or more, the alcoholic solution of sherwood oil, normal hexane alcoholic solution, alcoholized chloroform solution, ethyl acetate alcoholic solution, methyl acetate alcoholic solution one or more.Described alcoholic solution is methyl alcohol or ethanolic soln.
Described urea saturated solution is methyl alcohol or alcoholic acid urea saturated solution.
As described in (3) step, usedly contain the hydrolysate that linolenic raw material of fatty acid is oleum lini, perilla oil, Oleum Hippophae, microula oil, Chinese gooseberry seed oil, Fructus Zanthoxyli oil, root of Redsepal Eveningprimrose and blackcurrant oil.
As described in (3) step, the used linolenic acid lower member ester fatty acid ester raw material that contains is the alcoholysis product of oleum lini, perilla oil, Oleum Hippophae, microula oil, Chinese gooseberry seed oil, Fructus Zanthoxyli oil, root of Redsepal Eveningprimrose and blackcurrant oil.
Characteristics of the present invention
The present invention has following characteristics:
1. technology is simple, and production cost is low;
2. can obtain gamma-linolenic acid or alpha-linolenic acid or their lower member ester series products according to different raw materials;
3. good separating effect, the yield height can obtain each lipid acid or its ester class in the raw material simultaneously;
4. equipment manufacturing cost is low, is convenient to suitability for industrialized production;
5. process sanitation and hygiene, environmental protection.
Embodiment
Embodiment 1:
Take by weighing 5g urea, be dissolved in the solution of moisture 10wt% methyl alcohol, add the 50g alumina supporter, decompression rotation evaporate to dryness is produced the stationary phase that load has urea; Prepare the ethanolic soln that contains sherwood oil 10wt%, as moving phase; With the oleum lini ethanol alcoholysate of pipette, extract 2ml, last sample, column chromatography, obtain the Alpha-ethyl linolenate of content 87wt%.
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 30g silica-gel carrier, freezing stirred crystallization is filtered, and produces the stationary phase that load has urea; With dehydrated alcohol as moving phase; With the purple perilla hydrolyzate of pipette, extract 3ml, last sample, column chromatography, obtain the alpha-linolenic acid of content 95wt%.
Embodiment 3:
Take by weighing 50g 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 sherwood oil as moving phase; With the methyl alcohol alcoholysate of pipette, extract 3ml Fructus Zanthoxyli oil, last sample, column chromatography, obtain the alpha-linolenic acid methyl esters of content 83wt%.
Embodiment 4:
Take by weighing 60g urea, be dissolved in the 80wt% Virahol, be made into saturated solution, add the 6g absorbent charcoal carrier, the 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, as moving phase; With the hydrolyzate of pipette, extract 3ml micropore grass, last sample, column chromatography, obtain the alpha-linolenic acid of content 90wt%.
Embodiment 5:
Take by weighing 260g urea, be dissolved in the anhydrous methanol, be made into saturated solution, freezing and crystallizing filters, and the urea that obtains is as stationary phase; With normal hexane as moving phase; With the ethanol alcoholysis product of pipette, extract 2ml Oleum Hippophae, last sample, column chromatography obtains the Alpha-ethyl linolenate that content is 80wt%.
Embodiment 6:
Take by weighing 200g urea, be dissolved in the 95wt% methyl alcohol, be made into saturated solution, the rotation evaporate to dryness is pulverized gained urea, as stationary phase; Be made into the urea methanol saturated solution, as moving phase; With the hydrolyzate of pipette, extract 3ml kiwi oil, last sample, column chromatography, obtain the alpha-linolenic acid of content 92wt%.
Embodiment 7:
Take by weighing 300g urea, be dissolved in and contain in the 20wt% alcoholic acid methyl alcohol, be made into saturated solution, freezing and crystallizing filters, and pulverizes as stationary phase; Be made into 95wt% alcoholic acid urea saturated solution, as moving phase; With pipette, extract 3ml root of Redsepal Eveningprimrose ethanol alcoholysate, last sample, column chromatography, obtain the gamma-ethyl linolenate of content 90wt%.
Embodiment 8:
Take by weighing 50g urea, be dissolved in the anhydrous methanol, be made into saturated solution, add 50g silica gel, freezing and crystallizing filters, and makes the stationary phase that load has urea; Be made into and contain methyl alcohol 5wt% chloroformic solution, as moving phase; With the ethanol alcoholysate of pipette, extract 3ml blackcurrant oil, last sample, column chromatography, obtain containing gamma-ethyl linolenate and Alpha-ethyl linolenate total amount product at 85wt%.
Embodiment 9:
Take by weighing 50g urea, be dissolved in the methanol solution that contains the 10wt% Virahol, add the 50g aluminum oxide, the rotation evaporate to dryness makes the stationary phase that load has urea; Be made into the ethanolic soln that contains ethyl acetate 50wt%, as moving phase; With the methyl alcohol alcoholysate of pipette, extract 2ml oleum lini, last sample, column chromatography, obtain the product of the alpha-linolenic acid methyl esters of content 85wt%.
Embodiment 10:
Take by weighing 10g urea, be dissolved in the anhydrous methanol, be made into saturated solution, add 70g silica gel, add an amount of ethanol, allow urea crystals, filter, make the stationary phase that load has urea; Be made into the petroleum ether solution that contains ethyl acetate 50wt%, as moving phase; With the ethanol alcoholysate of pipette, extract 2ml oleum lini, last sample, column chromatography obtains the product that content is the Alpha-ethyl linolenate of 80wt%.
Embodiment 11:
Take by weighing 300g urea, be dissolved in the anhydrous methanol, be made into saturated solution, the rotation evaporate to dryness is pulverized as stationary phase; Be made into the urea saturated solution of methyl alcohol, as moving phase; With pipette, extract 3ml root of Redsepal Eveningprimrose hydrolysate, last sample, column chromatography obtains the gamma-linolenic acid that content is 95wt%.
Embodiment 12:
Take by weighing 300g urea, be dissolved in the anhydrous methanol, be made into saturated solution, add chloroform, allow the chloroform crystallization separate out, filter, as stationary phase; Be made into and reaffirm the weight ratio sherwood oil: ethanol: the solution of methyl alcohol=6: 2: 2, as moving phase; With pipette, extract 2ml root of Redsepal Eveningprimrose ethanol alcoholysate, last sample, column chromatography obtains the gamma-ethyl linolenate that content is 93wt%.
Claims (13)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710061440 CN100500632C (en) | 2007-01-19 | 2007-01-19 | Method for producing linolenic acid and lower esters of linolenic acid by urea column chromatography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710061440 CN100500632C (en) | 2007-01-19 | 2007-01-19 | Method for producing linolenic acid and lower esters of linolenic acid by urea column chromatography |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101016242A true CN101016242A (en) | 2007-08-15 |
| CN100500632C CN100500632C (en) | 2009-06-17 |
Family
ID=38725485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710061440 Active CN100500632C (en) | 2007-01-19 | 2007-01-19 | Method for producing linolenic acid and lower esters of linolenic acid by urea column chromatography |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100500632C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107382707A (en) * | 2017-08-03 | 2017-11-24 | 山西康惠中天医药科技有限公司 | A kind of method of efficiently purifying alpha linolenic acid |
| CN110105199A (en) * | 2019-05-23 | 2019-08-09 | 河南农业大学 | A kind of method of purification of woody alpha-linolenic acid used for intravenous injection |
| CN112774251A (en) * | 2019-11-27 | 2021-05-11 | 安徽华恒生物科技股份有限公司 | Method for separating acid and ester mixed solution |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095824C (en) * | 2000-04-13 | 2002-12-11 | 胡德甫 | Preparation method of high-purity alpha-linolenic acid |
| CN1394944A (en) * | 2001-07-11 | 2003-02-05 | 北京万博力科技发展有限公司 | Method for preparing alpha-ethyl linolenate from linseed oil by means of ester exchange |
| CN100369884C (en) * | 2004-11-30 | 2008-02-20 | 中国科学院山西煤炭化学研究所 | Method of separating alpha ethyl linolenate by cuprous chloride complexation adsorption |
-
2007
- 2007-01-19 CN CN 200710061440 patent/CN100500632C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107382707A (en) * | 2017-08-03 | 2017-11-24 | 山西康惠中天医药科技有限公司 | A kind of method of efficiently purifying alpha linolenic acid |
| CN110105199A (en) * | 2019-05-23 | 2019-08-09 | 河南农业大学 | A kind of method of purification of woody alpha-linolenic acid used for intravenous injection |
| CN112774251A (en) * | 2019-11-27 | 2021-05-11 | 安徽华恒生物科技股份有限公司 | Method for separating acid and ester mixed solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100500632C (en) | 2009-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5086111B2 (en) | Method for preparing a plant extract to treat skin disorders and promote wound healing | |
| KR100756128B1 (en) | How to selectively extract furan lipid and polyhydroxylated fatty alcohols of avocado | |
| JP2657056B2 (en) | How to enrich .GAMMA.-linolenic acid | |
| CN104688782B (en) | A kind of method of the high efficiency extraction triterpene active component from fuling peel | |
| CN101845362B (en) | Method for gathering oleic acid from tea-seed oil | |
| CN102247420B (en) | Preparation method and application of eclipta extract | |
| CN105175266A (en) | Method for extracting chlorogenic acid and caffeic acid from coffee beans | |
| CN100500632C (en) | Method for producing linolenic acid and lower esters of linolenic acid by urea column chromatography | |
| CN101429112B (en) | Method for distillation separation of mixture of nervonic acid and erucic acid from acer truncatum oil | |
| CN115894515A (en) | Method for integrated extraction, enrichment, separation and purification of effective components of ginkgo leaves in full industrial chain | |
| CN101973848A (en) | Method for separating and purifying solanesol by urea column chromatography | |
| JP2016532724A (en) | Medical composition of seed extract of Emblica officinalis and method for its preparation | |
| CN101967083A (en) | Method for separating and refining polyprenol in ginkgo biloba extract | |
| CN107298642B (en) | Extraction and purification method of 6-shogaol | |
| CN101486954B (en) | A kind of separation method of oleic acid and trans oleic acid, oleic acid ester and trans oleic acid ester | |
| CN109576048A (en) | The method extracted volatile oil from sunglo and extract sunglo polysaccharide and usnic acid simultaneously | |
| EP4349356A1 (en) | Method for the preparation of extracts enriched with saturated, monounsaturated and polyunsaturated long-chain fatty acids from tabebuia impetiginosa (lapacho) | |
| CN105669797A (en) | Method for separating burdock oil, arctiin, arctigenin, lappaol E and lappaol H from burdock | |
| CN102603845A (en) | Method for synthesizing and separating phytosterol saturated fatty acid esters and phytosterol unsaturated fatty acid esters | |
| KR101919387B1 (en) | Coix seed oil comprising 16 glycerides, formulation and application thereof | |
| CN100453519C (en) | A kind of production method of linolenic acid or lower ester of linolenic acid | |
| CN102786418B (en) | Chlorogenic acid brilliant II type sign and preparation method and apply in medicine and health products | |
| Gustafson et al. | Pycnanthus angolensis: bioactive compounds and medicinal applications | |
| CN100357358C (en) | Preparation method of lycopene | |
| CN107955054A (en) | A kind of method that film simultaneous reaction and separation prepares phytosterin ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240509 Address after: 030000 No.27 Taoyuan South Road, Taiyuan, Shanxi Province Patentee after: Shanxi Kelin Biotechnology Development Co.,Ltd. Country or region after: China Address before: 165 mailbox 030001, Shanxi City, Taiyuan Province Patentee before: INSTITUTE OF COAL CHEMISTRY, CHINESE ACADEMY OF SCIENCES Country or region before: China |
|
| TR01 | Transfer of patent right |