CN101774997A - Method for completely and continuously extracting natural vitamin E and phytosterol - Google Patents
Method for completely and continuously extracting natural vitamin E and phytosterol Download PDFInfo
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- CN101774997A CN101774997A CN201010104339A CN201010104339A CN101774997A CN 101774997 A CN101774997 A CN 101774997A CN 201010104339 A CN201010104339 A CN 201010104339A CN 201010104339 A CN201010104339 A CN 201010104339A CN 101774997 A CN101774997 A CN 101774997A
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Abstract
The invention discloses a method for completely and continuously extracting natural vitamin E and phytosterol, which comprises the following steps of: (1) using a leftover namely a deodorizing distillate generated in the production process of vegetable oil as a raw material, filtering the raw material to remove impurities and drying the raw material; (2) fully mixing the material processed by the step (1) with low-carbon monohydric alcohol, heating the mixture, and passing the mixture through a resin column; (3) performing pressurization to remove the low-carbon monohydric alcohol and water; (4) mixing the material obtained by the step (3) with alkaliferous low-carbon monohydric alcohol, heating the mixture, putting the mixture into a reaction kettle continuously to transform neutral oil into aliphatic ester; (5) adding acid into the mixture for neutralization; (6) washing the mixture until the mixture is neutral; and (7) crystallizing the mixture, filtering and separating the mixture to obtain solid phase coarse phytosterol and a liquid phase, and performing molecular distillation on the liquid phase to separate out fatty acid ester and the natural vitamin E. The method generates less water, can realize PLC controlled continuous production and has the advantages of low labor intensity, clean production environment, stable working index and high product yield, and the phytosterol has high purity.
Description
Technical field
The invention belongs to natural product biological extraction technology, relate to the method for a kind of full continuously extracting natural vitamin E and plant sterol.
Background technology
Natural VE extensively is present in the nature animal vegetable tissue, particularly in the oil of seed of plant and pulp, is a kind of faint yellow thick transparent liquid, and is colourless, tasteless, water insoluble, dissolves in organic solvent and oil such as ethanol, acetone, chloroform.Natural VE is having remarkable difference with sintetics aspect raw materials for production, opticity, density, the isomer composition, U.S. FDA is classified natural VE as " It is generally accepted safety " (GRAS, Generally Recognized As Safe) material has enhancing body immunologic function and anticancer; Neuroprotective system, skeletal muscle, retina and delay senility; Keep the normal function of cardiovascular systems etc.Be widely used in industries such as medicine, food, makeup and feed.
Plant sterol extensively is present in plant and the plant seed, is the important component of vegetable cell, has crucial physiological function.Plant sterol is a kind of white powder or crystal with opticity, is slightly soluble in acetone and ethanol under water insoluble, sour, the alkali, normal temperature, is dissolved in organic solvents such as ether, benzene, chloroform, ethyl acetate, sherwood oil and dithiocarbonic anhydride.Plant sterol can effectively reduce the effect of cholesterol in the blood, plays the effect of effective prevention and cardiovascular disordeies such as treatment hypertension and coronary heart disease; Have the anti-inflammatory action that is similar to crovaril and hydrocortisone, have similar acetylsalicylic acid febrifugal effect concurrently; Have the blocking-up carcinogens and bring out the function that cancer cells forms; Giving play to good physiological potency aspect skin-nourishing and the protection.Plant sterol is a kind of safe crude substance, is widely used in industries such as medicine, food, makeup, growth of animal agent and chemical industry.
Domestic production natural VE and plant sterol have formed certain scale at present, mainly extract in the tankage deodorization distillate (DD oil) that produces from production process of vegetable oil.Basic technology is: earlier DD oil is converted into fatty acid methyl ester with the methyl alcohol reaction with free lipid acid under the sulfuric acid catalysis condition, wash then pickling is fallen, under the base catalysis condition, neutral oil is converted into methyl esters again with the methyl alcohol reaction, neutralization washing again, liquid after handling is filtered to isolate sterol through crystallization, filtrated stock is passed through molecular distillation separating natural vitamin E and fatty acid methyl ester.Though this technology comparative maturity, the vitriol oil can cause serious corrosion to equipment, and this technology produces a large amount of waste water simultaneously, along with the reinforcement of environmental requirement, this technology will be banned or be eliminated, in addition, this process using be gap operating, production efficiency is lower, production environment is relatively poor.Domestic a kind of process for super-critical extracting also disclosed, this arts demand high pressure, production cost is higher; Another method adopts enzyme process catalyzed synthesis of fatty acid methyl esters to distill out natural VE then, though this method mild condition does not produce waste water, but the catalytic activity repeatability of enzyme is relatively poor, reaction times is longer, and production efficiency is lower, is not suitable for large-scale industrial production.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of waste water of generation few, labour intensity is low, production environment cleaning, production efficiency height, the full continuously extracting natural vitamin E that technic index is stable and product yield is high and purity is high and the method for plant sterol.
Technical scheme of the present invention is summarized as follows:
The method of full continuously extracting natural vitamin E and plant sterol comprises the steps:
(1) using the tankage deodorization distillate that produces from production process of vegetable oil is that raw material removes by filter impurity, and drying makes the mass content of water drop to 0.1%～0.5%;
(2) be 1: 0.5～5 ratio by volume, material and the low-carbon (LC) monohydroxy-alcohol thorough mixing that will handle through step (1) be heated to 50-80 ℃, then with the flow velocity of 0.1～2 times of resin volume per hour by the resin column of highly acidic resin is housed;
(3) low-carbon (LC) monohydroxy-alcohol and moisture are sloughed in decompression, make the mass content of water be controlled at 0.1%-0.5%;
(4) be 1: 0.1～1 ratio by volume, with step (3) material that obtains and the low-carbon (LC) monohydroxy-alcohol thorough mixing that contains alkali, be heated to 50～80 ℃, enter reactor continuously, stop 0.5～3h, make neutral oil be converted into lipid acid low-carbon (LC) monobasic alcohol ester, the mass concentration that contains alkali in the low-carbon (LC) monohydroxy-alcohol of alkali is 3%～5%;
(5) add acid and carry out online neutralization, making the pH value is 1～7;
(6) be washed to neutrality through water wash column;
(7) liquid after will washing carries out crystallization by crystallizer, and filtering separation obtains thick plant sterol of solid phase and liquid phase; The thick plant sterol of described solid phase carries out thermosol, hot filter, recrystallization, filtration and drying with 5-20 quality solvent doubly, obtains plant sterol; Described liquid phase is isolated lipid acid low-carbon (LC) monobasic alcohol ester and natural VE by molecular distillation.
The preferred D061 of the model of highly acidic resin, NKC-9, HD-8, D002, D006,005CR, CAT601, C005 or CAT600
The described alkali of step (4) can select KOH, NaOH, sodium methylate or sodium ethylate, also can select other alkali for use.
The described acid of step (5) can be selected sulfuric acid, hydrochloric acid, phosphoric acid, citric acid or acetic acid, also can select other acid for use.
The described solvent preferred alcohol of step (7), butanols, acetone, sherwood oil or ethyl acetate.
Reactor can be selected various types of reactors for use, preferred multistage laminar flow reactor.
Water wash column can be selected various types of water wash columns for use, preferred counter-current extraction water wash column.
Crystallizer can be selected various types of crystallizers for use, preferably contains rapid chilling section, the crystallizer of cooling section and growing the grain section at a slow speed.
The waste water that present method produces is few, it is 1/10 of classical acid alkaline process, whole production line can realize PLC control serialization production, labour intensity is low, the production environment cleaning, the production efficiency height, technic index is stable, the yield of natural VE and plant sterol reaches more than 85%, and the purity of plant sterol reaches more than 95%.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
The method of full continuously extracting natural vitamin E and plant sterol comprises the steps:
(1) using the tankage deodorization distillate that produces from production process of vegetable oil is that raw material removes by filter impurity, and drying makes the mass content of water drop to 0.3%;
(2) be 1: 1 ratio by volume, material and the methyl alcohol thorough mixing that will handle through step (1) be heated to 50 ℃, then with the flow velocity of 0.1 times of resin volume per hour by the resin column of D061 highly acidic resin is housed;
(3) methyl alcohol and moisture are sloughed in decompression, make the mass content of water be controlled at 0.3%;
(4) be 1: 0.5 ratio by volume, the material that step (3) is obtained and mass concentration are the methanol solution thorough mixing of 4% sodium methylate, are heated to 50 ℃, enter multistage laminar flow reactor continuously, and stop 3h makes neutral oil be converted into fatty acid methyl ester;
(5) add sulfuric acid and carry out online neutralization, making the pH value is 2;
(6) be washed to neutrality through the counter-current extraction water wash column;
(7) liquid after will washing by contain rapid chilling section, the crystallizer of cooling section and growing the grain section carries out crystallization at a slow speed, filtering separation obtains thick plant sterol of solid phase and liquid phase; The thick plant sterol of solid phase carries out thermosol, hot filter, recrystallization, filtration and drying with 10 quality ethanol doubly, obtains plant sterol; Liquid phase is isolated fatty acid methyl ester and natural VE by molecular distillation.
The purity 96.2% of natural VE yield 87.2%, plant sterol yield 86.5%, plant sterol.
Embodiment 2
The method of full continuously extracting natural vitamin E and plant sterol comprises the steps:
(1) using the tankage deodorization distillate that produces from production process of vegetable oil is that raw material removes by filter impurity, and drying makes the mass content of water drop to 0.1%;
(2) be 1: 3 ratio by volume, material and the ethanol thorough mixing that will handle through step (1) be heated to 60 ℃, then with the flow velocity of 1 times of resin volume per hour by the resin column of NKC-9 highly acidic resin is housed;
(3) ethanol and moisture are sloughed in decompression, make the mass content of water be controlled at 0.1%;
(4) be 1: 0.1 ratio by volume, the material that step (3) is obtained and mass concentration are the ethanolic soln thorough mixing of 3% sodium ethylate, are heated to 60 ℃, enter reactor continuously, and stop 2h makes neutral oil be converted into fatty-acid ethyl ester;
(5) add hydrochloric acid and carry out online neutralization, making the pH value is 7;
(6) be washed to neutrality through water wash column;
(7) liquid after will washing carries out crystallization by crystallizer, and filtering separation obtains thick plant sterol of solid phase and liquid phase; The thick plant sterol of solid phase carries out thermosol, hot filter, recrystallization, filtration and drying with 20 quality butanols doubly, obtains plant sterol; Liquid phase is isolated fatty-acid ethyl ester and natural VE by molecular distillation.
The purity 97.4% of natural VE yield 86.7%, plant sterol yield 85.8%, plant sterol.
Embodiment 3
The method of full continuously extracting natural vitamin E and plant sterol comprises the steps:
(1) using the tankage deodorization distillate that produces from production process of vegetable oil is that raw material removes by filter impurity, and drying makes the mass content of water drop to 0.5%;
(2) be 1: 0.5 ratio by volume, material and the 1-propyl alcohol thorough mixing that will handle through step (1) be heated to 70 ℃, then with the flow velocity of 1.5 times of resin volumes per hour by the resin column of HD-8 highly acidic resin is housed;
(3) 1-propyl alcohol and moisture are sloughed in decompression, make the mass content of water be controlled at 0.5%;
(4) be 1: 1 ratio by volume, the material that step (3) is obtained and mass concentration are the 1-propanol solution thorough mixing of 5% KOH, are heated to 70 ℃, enter reactor continuously, and stop 1h makes neutral oil be converted into the lipid acid propyl ester;
(5) add phosphoric acid and carry out online neutralization, making the pH value is 1;
(6) be washed to neutrality through water wash column;
(7) liquid after will washing carries out crystallization by crystallizer, and filtering separation obtains thick plant sterol of solid phase and liquid phase; The thick plant sterol of solid phase carries out thermosol, hot filter, recrystallization, filtration and drying with 5 quality acetone doubly, obtains plant sterol; Liquid phase is isolated lipid acid propyl ester and natural VE by molecular distillation.
The purity 97.3% of natural VE yield 89.3%, plant sterol yield 87.9%, plant sterol.
Embodiment 4
The method of full continuously extracting natural vitamin E and plant sterol comprises the steps:
(1) using the tankage deodorization distillate that produces from production process of vegetable oil is that raw material removes by filter impurity, and drying makes the mass content of water drop to 0.4%;
(2) be 1: 5 ratio by volume, material and the 1-amylalcohol thorough mixing that will handle through step (1) be heated to 80 ℃, then with the flow velocity of 2 times of resin volumes per hour by the resin column of D002 highly acidic resin is housed;
(3) 1-amylalcohol and moisture are sloughed in decompression, make the mass content of water be controlled at 0.4%;
(4) be 1: 0.6 ratio by volume, the material that step (3) is obtained and mass concentration are the 1-amyl alcohol solution thorough mixing of 4% NaOH, are heated to 80 ℃, enter reactor continuously, and stop 0.5h makes neutral oil be converted into the lipid acid pentyl ester;
(5) adding citric acid carries out online neutralization, and making the pH value is 3;
(6) be washed to neutrality through water wash column;
(7) liquid after will washing carries out crystallization by crystallizer, and filtering separation obtains thick plant sterol of solid phase and liquid phase; The thick plant sterol of solid phase carries out thermosol, hot filter, recrystallization, filtration and drying with 12 quality sherwood oil doubly, obtains plant sterol; Liquid phase is isolated lipid acid pentyl ester and natural VE by molecular distillation.
The purity 98.2% of natural VE yield 90.5%, plant sterol yield 89.1%, plant sterol.
Citric acid in the present embodiment also can substitute as oxalic acid or Citric Acid with acetic acid or other acid.
Sherwood oil in the present embodiment also can substitute with ethyl acetate.
The model of the highly acidic resin in the present embodiment also can select for use D006,005CR, CAT601, C005 or CAT600 to substitute.
Claims (8)
1. the method for full continuously extracting natural vitamin E and plant sterol is characterized in that comprising the steps:
(1) using the tankage deodorization distillate that produces from production process of vegetable oil is that raw material removes by filter impurity, and drying makes the mass content of water drop to 0.1%～0.5%;
(2) be 1: 0.5～5 ratio by volume, material and the low-carbon (LC) monohydroxy-alcohol thorough mixing that will handle through step (1) be heated to 50-80 ℃, then with the flow velocity of 0.1～2 times of resin volume per hour by the resin column of highly acidic resin is housed;
(3) low-carbon (LC) monohydroxy-alcohol and moisture are sloughed in decompression, make the mass content of water be controlled at 0.1%-0.5%;
(4) be 1: 0.1～1 ratio by volume, with step (3) material that obtains and the low-carbon (LC) monohydroxy-alcohol thorough mixing that contains alkali, be heated to 50～80 ℃, enter reactor continuously, stop 0.5～3h, make neutral oil be converted into lipid acid low-carbon (LC) monobasic alcohol ester, the mass concentration that contains alkali in the low-carbon (LC) monohydroxy-alcohol of alkali is 3%～5%;
(5) add acid and carry out online neutralization, making the pH value is 1～7;
(6) be washed to neutrality through water wash column;
(7) liquid after will washing carries out crystallization by crystallizer, and filtering separation obtains thick plant sterol of solid phase and liquid phase; The thick plant sterol of described solid phase carries out thermosol, hot filter, recrystallization, filtration and drying with 5-20 quality solvent doubly, obtains plant sterol; Described liquid phase is isolated lipid acid low-carbon (LC) monobasic alcohol ester and natural VE by molecular distillation.
2. the method for full continuously extracting natural vitamin E according to claim 1 and plant sterol is characterized in that described low-carbon (LC) monohydroxy-alcohol is the monohydroxy-alcohol of C1～C5.
3. the method for full continuously extracting natural vitamin E according to claim 1 and plant sterol, the model that it is characterized in that described highly acidic resin is D061, NKC-9, HD-8, D002, D006,005CR, CAT601, C005 or CAT600.
4. the method for full continuously extracting natural vitamin E according to claim 1 and plant sterol is characterized in that the described alkali of described step (4) is KOH, NaOH, sodium methylate or sodium ethylate.
5. the method for full continuously extracting natural vitamin E according to claim 1 and plant sterol is characterized in that the described acid of described step (5) is sulfuric acid, hydrochloric acid, phosphoric acid, citric acid or acetic acid.
6. the method for full continuously extracting natural vitamin E according to claim 1 and plant sterol is characterized in that the described solvent of described step (7) is ethanol, butanols, acetone, sherwood oil or ethyl acetate.
7. the method for full continuously extracting natural vitamin E according to claim 1 and plant sterol is characterized in that described reactor is multistage laminar flow reactor.
8. the method for full continuously extracting natural vitamin E according to claim 1 and plant sterol is characterized in that described water wash column is the counter-current extraction water wash column.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074165A (en) * | 2013-01-18 | 2013-05-01 | 天津大学 | Continuous ester interchange reaction method and reactor in production process of natural vitamin E and phytosterin |
| CN104151282A (en) * | 2014-08-14 | 2014-11-19 | 山东圣地嘉禾生物工程有限公司 | Method for preparing natural vitamin E and phytosterol with resin absorption method |
| CN105016956A (en) * | 2014-04-23 | 2015-11-04 | 中粮营养健康研究院有限公司 | Squalene extracting method |
| CN105777477A (en) * | 2014-12-23 | 2016-07-20 | 中粮集团有限公司 | Method for extracting high-purity squalene |
| CN114686297A (en) * | 2022-04-01 | 2022-07-01 | 中粮工科(西安)国际工程有限公司 | Method for efficiently retaining natural VE and phytosterol in walnut oil |
| CN114773421A (en) * | 2022-05-25 | 2022-07-22 | 沧州市宝来金康生物科技股份有限公司 | Novel process for extracting high-purity phytosterol by utilizing biological polar resin and continuous counter-current liquid-solid extraction |
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2010
- 2010-02-02 CN CN2010101043398A patent/CN101774997B/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074165A (en) * | 2013-01-18 | 2013-05-01 | 天津大学 | Continuous ester interchange reaction method and reactor in production process of natural vitamin E and phytosterin |
| CN105016956A (en) * | 2014-04-23 | 2015-11-04 | 中粮营养健康研究院有限公司 | Squalene extracting method |
| CN105016956B (en) * | 2014-04-23 | 2017-08-08 | 中粮营养健康研究院有限公司 | A kind of method for extracting squalene |
| CN104151282A (en) * | 2014-08-14 | 2014-11-19 | 山东圣地嘉禾生物工程有限公司 | Method for preparing natural vitamin E and phytosterol with resin absorption method |
| CN105777477A (en) * | 2014-12-23 | 2016-07-20 | 中粮集团有限公司 | Method for extracting high-purity squalene |
| CN105777477B (en) * | 2014-12-23 | 2019-02-22 | 中粮集团有限公司 | A method of extracting high-purity squalene |
| CN114686297A (en) * | 2022-04-01 | 2022-07-01 | 中粮工科(西安)国际工程有限公司 | Method for efficiently retaining natural VE and phytosterol in walnut oil |
| CN114773421A (en) * | 2022-05-25 | 2022-07-22 | 沧州市宝来金康生物科技股份有限公司 | Novel process for extracting high-purity phytosterol by utilizing biological polar resin and continuous counter-current liquid-solid extraction |
| CN114773421B (en) * | 2022-05-25 | 2024-03-01 | 沧州市宝来金康生物科技股份有限公司 | Novel process for extracting high-purity phytosterol by using bio-polar resin and continuous reflux liquid-solid extraction |
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