CN1948261A - Enriching of alpha-linolenic acid by physical-method dissociating fat - Google Patents
Enriching of alpha-linolenic acid by physical-method dissociating fat Download PDFInfo
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- CN1948261A CN1948261A CNA2006100222267A CN200610022226A CN1948261A CN 1948261 A CN1948261 A CN 1948261A CN A2006100222267 A CNA2006100222267 A CN A2006100222267A CN 200610022226 A CN200610022226 A CN 200610022226A CN 1948261 A CN1948261 A CN 1948261A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The present invention relates to a technological process for enriching alpha-linolenic acid by utilizing physical method to dissociate tallowseed and silkworm chrysalis oil. Said technological process includes the following three steps: (1), impregnating, removing protein and tanking oil; pulverizing silkworm chrysalis and tallowseed, screening, removing shell to obtain powder material, using ethyl alcohol to impregnate said powder material, making centrifugal solid-liquid separation, removing solid crude protein and obtain liquid oil; (2), extracting and dissociating saturated fatty acid and taking n-3 series olefine acid mixture: making the above-mentioned obtained oil be fed into a supercritical extraction apparatus, at the same time injecting liquid CO2, liquid nitrogen and ethyl alcohol, making static extraction, regulating and controlling pressure, making temperature dynamic extraction for 4-6 h, making collection by layers, firstly collecting bottom layer colored macromolecular saturated fatty acid, then collecting colorless upper layer n-3 series fatty olefine acid and low-grade alcohol ester mixture, in which ALA content is 63-72%; and (3), film evaporating and dissociating low-grade alcohol ester: preheating n-3 series olefine oil mixture and feeding said mixture into a multistage molecular film evaporating machine, making constant temperature evaporation, vacuum controlling whole body balance, making the volatile low-grade alcohol ester be passed through cooling surface and cooled into liquor, ad flowed into the collecting flask A; and making the low-volatility heavy component ALA be flowed into collecting flask B along the inner wall of heating pipe, its ALA content is 93-97%.
Description
1. technical field
The invention belongs to the classical technical field of physics method disassociation grease molecular engineering.Be specifically related to other lipid acid in the physics method disassociation grease and enriching of alpha-linolenic operational path and coordinative composition of equipments.
2. background technology
1) physics method disassociation grease and enrichment alpha-linolenic acid research application background
Alpha-linolenic acid (a-Linlenic acid.ALA) molecular formula C18H3002, chemical name is along 9 suitable 12 suitable 15-punicic acid (Δs
9.12.15: 18.3) being present in the specified plant aquatic organism, is the indispensable fatty acid that human body generally lacks.ALA is the structured material of each cell membranes in tissue of human body, the most important product timnodonic acid of its metabolism (EPA.C20 ω-5) is the moiety of leukotriene prostaglandin(PG), and docosahexenoic acid (DHA C22 ω 6) is the important composition composition of brain, retina, neural system phosphatide.Have important biology, pharmic function according to big quantity research reported in literature: ALA and meta-bolites thereof to maintaining vital movement: highly increase intelligence the height vision protection; Suppress cardiovascular and cerebrovascular diseases, step-down, reducing blood-fat; Delay senility, check cancer generation and transfer; Prevention myocardial infarction, cerebral infarction.In view of its importance, the 9 years Food and Argriculture OrganizationFAO and the World Health Organization unite and issue a statement: do special the popularization in world wide, once starting research ALA upsurge.Determined that now n-3 is that octadecenoic acid is with other lipid acid 1: 5 title side of best proportioning breast milk ratio in ingesting.Countries such as day, moral, method, U.S. system of having made laws is marked to be defined in the certain food and must be added an amount of ALA, and particularly old age, infant foods are such as milk powder.Japan replenishes 2 and restrains the 25-30% that on average lengthens the life in the people ingests flat every day./ 10th of a not enough breast milk ratio of ALA that Chinese people is flat in ingesting.Study at the experimental stage always, the import price costliness, the condition of lack using, this invention is gone through the research in 10 years, intends meter 2007 and produces 300 tons of ALA listings per year.
2) the domestic and international state of the art of association area
(1) research that has entered the physiological metabolism approach abroad: some countries are by development of resources, industrialization, legislation system mark changes the research of grease physiological metabolism in human body over to, especially the physiological metabolism of ALA is subjected to the reverse action of saturated fatty acid metabolism disorder and the relation of some disease, and these achievements in research will be brought major reform to human food prods's structure.
3) the domestic technique present situation totally is in the experimental study stage
Domestic linolenic acid has extensively been carried out research, compile representative article as: the Zhang Haiman of Tsing-Hua University " function of α-industry fiber crops acid; resource and production method ", Zhengzhou Engineering College Li Gui China " the method research for preparing alpha-linolenic acid by linolic acid ", float " the orthogonal test research that urea adduct method separates the alpha-linolenic acid in the Fructus Zanthoxyli oil " is opened by southwest agricultural university, the Zhang Junmei of Shandong University " alpha-linolenic acid extraction process and composition analysis in the silkworm chrysalis ", the Hu Xiaojun of academy of agricultural sciences, Shanxi " research of freezing acetone method purification alpha-linolenic acid ", horse Berlin, agricultural University of Science and Technology, northwest " supercritical CO
2The extraction bark of eucommia research ", the Zheng of University Of Tianjin Tao " research of molecular distillation purification alpha-linolenic acid ".Combine and comment these present Research methods single, generally belong to experimental data, purity is low.From subjective analysis: grease is glycerine three acid mixtures, mainly by macromolecular saturated fatty acid, n-3 is an olefin(e) acid, rudimentary alcohol ester is formed, urea embedding method, supercritical fluid extraction can only separate big sub-saturated fatty acid, and molecular distillation is meeting separate lower alcohol ester only, and domestic all is research methods, therefore ALA content is confined to about 60%, and it is not enough to illustrate that the research method degree of depth exists; From objective analysis, the education and scientific research policy issue, scientific research personnel's custom is done experiment, fetches data, and writes article.Here it is, and the long duration can not stride forward industrial basic place.
4) other technology
Inquiring into laser, infrared rays cutting tri-glyceride mixture ester bond to each other at present.
3. summary of the invention
At above-mentioned deficiency, the objective of the invention is to create the industrial operational path of linolenic acid and obtain the high yield of ALA, high purity, no hazard residue thing does not endanger environment, and cost is low, and wide resource promotes to form the emerging new industry of ALA.
To achieve these goals, technical solution of the present invention is: 1) adopt physics method dissociate step by step lipid acid in the grease tri-glyceride mixture and enriching of alpha-linolenic operational path, its feature is realized by the following step: (1) dipping removes albumen and gets grease: get the Chinese tallow tree seed, silkworm chrysalis is rich in linolenic resource, pulverize through GFS type Highefficientpulverizer, BT type multi-layer type vibration branch screens out shell, get about 120 months meal, reclaim ethanol after adding alcohol dipping, the high speed centrifugation solid-liquid separation, the solid master contains crude protein, gets colourless grease; (2) extraction disassociation tri-glyceride is that saturated fatty acid and n-3 are the olefin(e) acid mixture: grease is imported in the overcritical body abstraction instrument, injected liquid CO simultaneously
2, liquid nitrogen, ethanol make fluid, static extracting 1 hour, regulation and control pressure, temperature dynamic extraction 4～6 hours, the thing that will not dissociate in the extraction process enters ISCO type gathering system, adopts batch to be extracted into terminal point, pumps into to leave standstill after separating funnel fully stirs and waits to be divided into four layers, collect saturated fatty acid successively, n-3 is olefin(e) acid mixture, ethanol, CO
2, wherein n-3 is the ALA content 63-72% in the olefin(e) acid mixture; (3) film molecule evaporation disassociation removes low-carbon-ester and gets the high purity linolenic acid: with n-3 is in the olefin(e) acid mixture preheating input molecular film rapid steamer, evaporation at constant temperature, by the vacuum degree control population equilibrium, volatile light constituent (low-carbon-ester) is cooled to liquid through cooling surface and flows into receiving flask A, the heavy constituent that relative volatility is lower flow into receiving flask B along the heating tube inwall, change dual evaporation over to until eliminating low-carbon-ester, ALA content reaches 93-97%.
4. embodiment reaches for example
(1) mode: follow the ascending methods that enlarge step by step of science and technology item technical transform rule.
(2) be example with 500 liters of supporting pilot scales of supercritical fluid extraction instrument, performing step is as follows: (1) dipping removes crude protein and gets grease: take by weighing 2000 kilograms of silkworm chrysalises, pulverize through GFS type Highefficientpulverizer, importing BT type multi-layer type vibrosieve into screens out shell and gets 120 order meals, added 2 times of ethanol (w/w) dipping 24 hours, reclaim ethanol, the high speed centrifugation solid-liquid separation, get 45 kilograms of solids crude protein 12s, 205 kilograms of greases, palmitinic acid wherein, 24.36% oleic acid 4.74%, linolenic acid 34.5%, alpha-linolenic acid 33.4%; (2) extraction disassociation tri-glyceride mixture removes saturated fatty acid, and getting n-3 is the olefin(e) acid mixture: in 205 kilograms of greases input supercritical extraction instrument, inject liquid CO simultaneously
2, each 100 kilograms of liquid nitrogen, ethanol, static extracting 1 hour, regulation and control pressure 20Mpa, 45 ℃ of constant temperature, dynamic extraction 5 hours pumps into to leave standstill after separating funnel fully stirs and treats obviously to be divided into four layers, and 44 kilograms of saturated fatty acids are collected in layering from bottom to up, n-3 is 137 kilograms in an olefin(e) acid mixture, ethanol, CO
2(3) the film molecule evaporates the low-carbon-ester enrichment high purity linolenic acid that dissociates: the rotor stirring system that removes VLK type molecular distillating machine with many-level molecule thin film evaporation machine.With n 3 is 50 ℃ of olefin(e) acid mixture preheatings, at the uniform velocity import in 1 grade of generating tube, and 105 ℃ of evaporations of constant temperature, regulation and control vacuum tightness 2.0pa keeps whole machine balancing, and volatile light constituent (being low-carbon-ester) is cooled to liquid through cooling surface and flows into receiving flask A; The heavy constituent that relative volatility is lower are that n-3 is that olefin(e) acid flows into receiving flask B along the heating tube inwall, change 2 grades of evaporations over to, up to eliminating low-carbon-ester, linolenic acid content 96.86%, 98.84 kilograms of quality, 27.3 kilograms of collection A bottle quality.
Pressing the method for GB regulation measures: acid number, iodine number, peroxide value.Meet GB level index.
Gas Chromatographic Determination n-3 is the olefin(e) acid component: oleic acid 7.48%, and linolenic acid 48.81%, alpha-linolenic acid 47.7%, the rate of recovery 71.5% reclaims 71.3 kilograms in other lipid acid.
4. the beneficial effect of the technology of the present invention
1) according to producing 300 tons of ALA budgetary estimates per year, consume 6000 tons of silkworm chrysalises, 7,000 ten thousand yuan of import equipment investment Renminbi adopt 2,000 ten thousand yuan of this operational path support equipment device Renminbi, 2.4 hundred million yuan of annual value of production, total cost, 1.09 hundred million yuan, 1.31 hundred million yuan of benefits.
2) two class by products utilize: one is that 6000 tons of silkworm chrysalises are isolated 3735 tons of silkworm chrysalis crude protein, application invention patented technology (ZL 99114897.5) can be produced 50,000 tons of mixed feeds, 8,000 ten thousand yuan of the output values, perhaps the L Serine is extracted in the silkworm chrysalis hydrolysis, yield 3% produces 112.05 tons, 5602.5 ten thousand yuan of the output values, two product benefits are all more than 50%; Two is that 600 greases disassociation collection n-3 is 209 tons in other outer lipid acid of olefin(e) acid, appliable plant grease develop energy technology, and through saponification, 300 tons of fatty-acid ethyl esters, about 1,000,000 yuan of the output values are produced in esterification.
3) this technology guarantees that suitability for industrialized production do not have harm to ecotope: whole technological process only adds nontoxic CO
2, liquid nitrogen, ethanol do outside the fluid, adds the compound that chemical reaction takes place in affiliation without any link, the pressure thermal distillation is all in physical extent; Can not cause the variation of physical property, product does not have the agent of appearance residue, has kept the material physiologically active; Comprehensive utilization application invention patented technology and new technique handle poor slag, mash thoroughly, environment, economic benefit be all good.
4) this Technology is created and is applicable to the industrial coordinative composition of equipments device of linolenic acid: the gathering system device that replaces ISCO type supercritical fluid extraction instrument with separating funnel, with molecular film stage evaporation unit, replace the rotor stirring system of VLK type molecular distillating machine.First batch of at home foundation is suitable for ALA equipment of industrial product corollary apparatus.
Industrial production major equipment instrument: Highefficientpulverizer, multi-layer type vibration sub-sieve, supercentrifuge, remodeling supercritical fluid extraction instrument, many-level molecule thin film evaporation unit, high-pressure liquid phase or gas chromatograph.
5. several technology specify
1) sets up linolenic acid quality index technical problem: state functionaries's not legislation as yet at present, issuing standard.In view of product goes on the market after will doing nutrition, medicine, function test, with reference to international indicator, work out enterprise's linolenic acid quality index, present functional department approval back and implement.
2) this technical applicationization---the suitability for industrialized production linolenic acid helps the technical development of correlative technology field, stand-alone development protein, and the technical field of lipid acid is extensive.Fully utilize in this technical field, reduce cost significantly, economic benefit must promote technical development.
Claims (4)
1. physics method disassociation grease and the operational path of enrichment alpha-linolenic acid: it is characterized in that separating earlier crude protein in the specific animal and plant, get grease tri-glyceride mixture, remove saturated fatty acid and low-carbon-ester and the enrichment high-purity alpha-linolenic acid through the substep disassociation.The specific implementation step: 1) the dipping protein isolate is got grease tri-glyceride mixture: silkworm chrysalis, Chinese tallow tree seed screen out shell and get 100～140 months meals through pulverizing, branch, after adding alcohol dipping distillation recovery ethanol, the centrifugal solid-liquid separation removes solids crude albumen and gets liquid fat; 2) extracting the saturated fatty acid collection n-3 that dissociates is olefin(e) acid and low-carbon-ester mixture: in grease metering input supercritical fluid extraction instrument, inject liquid CO simultaneously
2, liquid nitrogen, ethanol do fluid, static extracting 15～40 minutes, according to rerum natura boiling point regulation and control pressure 20-45mpa, 30-45 ℃ of material, dynamic extraction 4～6 hours; Be discharged into to leave standstill after the separatory bucket fully stirs and treat CO
2, ethanol, n-3 is a fatty acid mixt, the obvious layering of macromole saturated fatty acid is collected, wherein ALA content 62-73%; 3) the many-level molecule thin film evaporation low-carbon-ester that dissociates: with n-3 is that 40-70 ℃ of fatty acid mixt preheating at the uniform velocity is pressed in the pipe of molecular film distilling machinery, keep 90～110 ℃ of evaporations, modulation vacuum tightness 0.5～4.0pa guarantees whole machine balancing, and volatile low-carbon-ester is cooled to liquid through cooling surface and flows into receiving flask A; Heavy constituent-master that relative volatility is lower contains ALA and flows into receiving flask B along the heating tube inwall, and distillation is heavily covered in heavy constituent, and until being coated with volatile to the greatest extent light constituent, ALA content reaches 93～97%.
2. operational path according to claim 1 is characterized in that: use CO simultaneously
2, liquid nitrogen, ethanol make the fluid of supercritical extraction, utilized every kind of fluid liberation degree sum, reduces 1/2 of pressure in the fluid extraction process; For the funnel separatory provides condition, be that the lipid acid low-carbon-ester separates with the macromole saturated fatty acid with n-3 to greatest extent simultaneously, improved the yield efficient of supercritical fluid extraction.
3. according to claim 1 and 2,3 described operational paths, it is characterized in that: be efficient extn two class by products: the in-depth of two kinds of methods of crude protein utilize approach: the one, use and have intellecture property ZL 9911897.5 patent of invention technical transform complete feeds or extract L-Serine (L-Ser) with ion-exchange absorption; The 2nd, the lipid acid in the grease dissociation process except that n-3 is lipid acid, with saponification, fatty-acid ethyl ester is produced in esterification; The nontoxic substitute energy of doing.
4. according to the described operational path of claim 1-3, it is characterized in that: the gathering system device that substitutes ISCO type supercritical extraction instrument with separating funnel; The rotor stirring system of cancellation VLK type molecular distillating machine adopts classification molecular film evaporation unit, creates to be fit to the coordinative composition of equipments device that this operational path is realized suitability for industrialized production, promotes domestic linolenic acid industry to stride forward the new stage.
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| CNB2006100222267A CN100457707C (en) | 2006-11-09 | 2006-11-09 | Enriching of alpha-linolenic acid by physical-method dissociating fat |
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| CNB2006100222267A CN100457707C (en) | 2006-11-09 | 2006-11-09 | Enriching of alpha-linolenic acid by physical-method dissociating fat |
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| CN1948261A true CN1948261A (en) | 2007-04-18 |
| CN100457707C CN100457707C (en) | 2009-02-04 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102342927A (en) * | 2011-07-22 | 2012-02-08 | 十堰天翔茧丝生化有限公司 | Method for extracting silkworm chrysalis extract |
| CN104725216A (en) * | 2015-02-12 | 2015-06-24 | 湖北华龙生物制药有限公司 | Method for purifying and separating high-purity alpha-linolenic acid and linoleic acid from Chinese tallow kernel oil |
| US11872201B2 (en) | 2018-06-21 | 2024-01-16 | Nuseed Nutritional Us Inc. | DHA enriched polyunsaturated fatty acid compositions |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095824C (en) * | 2000-04-13 | 2002-12-11 | 胡德甫 | Process for preparing high-purity alpha-linolenic acid |
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2006
- 2006-11-09 CN CNB2006100222267A patent/CN100457707C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102342927A (en) * | 2011-07-22 | 2012-02-08 | 十堰天翔茧丝生化有限公司 | Method for extracting silkworm chrysalis extract |
| CN104725216A (en) * | 2015-02-12 | 2015-06-24 | 湖北华龙生物制药有限公司 | Method for purifying and separating high-purity alpha-linolenic acid and linoleic acid from Chinese tallow kernel oil |
| US11872201B2 (en) | 2018-06-21 | 2024-01-16 | Nuseed Nutritional Us Inc. | DHA enriched polyunsaturated fatty acid compositions |
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| Publication number | Publication date |
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| CN100457707C (en) | 2009-02-04 |
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