CN103012467A - Method for preparing high-purity acetylation soybean phospholipid under CO2 supercritical state - Google Patents
Method for preparing high-purity acetylation soybean phospholipid under CO2 supercritical state Download PDFInfo
- Publication number
- CN103012467A CN103012467A CN2011102784857A CN201110278485A CN103012467A CN 103012467 A CN103012467 A CN 103012467A CN 2011102784857 A CN2011102784857 A CN 2011102784857A CN 201110278485 A CN201110278485 A CN 201110278485A CN 103012467 A CN103012467 A CN 103012467A
- Authority
- CN
- China
- Prior art keywords
- soybean phospholipid
- highly acetylated
- acetylation
- supercritical state
- preparation
- 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.)
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- 238000000034 method Methods 0.000 title claims abstract description 64
- JLPULHDHAOZNQI-ZTIMHPMXSA-N 1-hexadecanoyl-2-(9Z,12Z-octadecadienoyl)-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCC\C=C/C\C=C/CCCCC JLPULHDHAOZNQI-ZTIMHPMXSA-N 0.000 title claims abstract description 40
- 239000008347 soybean phospholipid Substances 0.000 title claims abstract description 40
- 230000021736 acetylation Effects 0.000 title abstract 12
- 238000006640 acetylation reaction Methods 0.000 title abstract 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000012512 characterization method Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 7
- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 abstract description 5
- 239000012530 fluid Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract 1
- 150000003904 phospholipids Chemical class 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 8
- 238000007385 chemical modification Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- JZNWSCPGTDBMEW-UHFFFAOYSA-N Glycerophosphorylethanolamin Natural products NCCOP(O)(=O)OCC(O)CO JZNWSCPGTDBMEW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000008104 phosphatidylethanolamines Chemical class 0.000 description 2
- 150000003905 phosphatidylinositols Chemical class 0.000 description 2
- 229940067626 phosphatidylinositols Drugs 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- PORPENFLTBBHSG-MGBGTMOVSA-N 1,2-dihexadecanoyl-sn-glycerol-3-phosphate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(O)=O)OC(=O)CCCCCCCCCCCCCCC PORPENFLTBBHSG-MGBGTMOVSA-N 0.000 description 1
- 238000004965 Hartree-Fock calculation Methods 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The present invention provides a method for preparing high-purity acetylation soybean phospholipid under a CO2 supercritical state. According to the present invention, a transparent phospholipid is adopted as a raw material, and an acetylation method is selected to modify soybean phospholipid under a CO2 supercritical state to obtain high-purity acetylation soybean phospholipid; influence on an acetylation rate by an acetic anhydride amount, a reaction temperature, a reaction time, a reaction pH value and different acetylation conditions are researched; the CO2 supercritical fluid has advantages of low viscosity, large diffusion coefficient, high density, good solubility property and mass transfer property of the liquid and the gas, such that reaction efficiency can be improved in the field of high-purity soybean phospholipid refinement, phosphatidylcholine content increase is easily achieved, and substantial energy saving can be achieved, wherein the high-purity acetylation soybean phospholipid with an acetylation rate of 93.2% can be finally obtained, and the acetylation rate of the obtained high-purity acetylation soybean phospholipid prepared under the CO2 supercritical state is significantly higher than the acetylation rate of the high-purity acetylation soybean phospholipid prepared under the conventional condition.
Description
Technical field:
The present invention relates to the processing of farm products field, be specifically related to a kind of at CO
2The method of the highly acetylated soybean phospholipid of preparation under the supercritical state, the preparation of using highly acetylated soybean phospholipid.
Background technology:
Concentrated soybean phospholipid is a kind of faint yellow or translucent thick liquid matter of light brown, becomes branch to form by phosphatidylcholine (PC), phosphatidylethanolamine (PE), phosphatidylinositols (PI) and phosphatidic acid etc.Phosphatide is a kind of well behaved natural surface active agent; have the effects such as emulsification, softening, wetting, dispersion, infiltration, solubilising, reducing blood-fat, protection liver, beauty treatment; because it has good physicochemical property and physiological function, has been widely used in the aspects such as food, medicine, makeup.Phosphatide phosphatide is during as emulsifying agent, and its HLB value can only be as w/o type emulsifying agent about 4, and this has just limited its use range.It can carry out chemical modification by acidylate, hydrogenation, phthalein and enzymic hydrolysis, and chemical modification can be improved thermotolerance, emulsifying property and the dispersiveness in solution system of phosphatide.Phosphatide through chemical modification has the characteristics such as wetting ability is strong, HLB value height, good stability, and it has changed former soybean phospholipid and has met the molten characteristics of shipwreck.
Supercutical fluid (SCFs), it had both had the physical property such as the density similar to gas, viscosity, spread coefficient, had again the characteristic close with liquid concurrently, was the material that is in the intermediateness between gaseous state and the liquid state.This fluid has the advantage of liquids and gases concurrently: viscosity is little, spread coefficient is large, density is large, has good dissolution characteristics and mass transfer characteristic, and responsive especially to temperature and pressure at Near The Critical Point.Supercritical CO
2Intermolecular forces very little, be similar to gas, and density is very large, close to liquid, be a kind of gas-liquid regardless of state, do not have phase interface, just do not have phase border effect yet, help to improve reaction efficiency, and can be significantly energy-conservation.Aspect the purifying high-purity soybean phospholipid, the processing condition of rationally controlling supercritical fluid extraction are conducive to the raising of phosphatidylcholine content.
Summary of the invention:
The present invention selects acetylizad method that soybean phospholipid is carried out modification under supercritical state, thereby obtains the method for highly acetylated soybean phospholipid take transparent phosphatide as raw material.At CO
2The method of the highly acetylated soybean phospholipid of preparation realizes by following steps under the supercritical state: one, the preparation of transparent phosphatide.Two, at CO
2Under the supercritical state it is carried out acylation reaction.Three, the mensuration of acidylate rate.The optimization of four, acetylize condition.Five, at CO
2The comparison of the highly acetylated phosphatide for preparing under the supercritical state and the highly acetylated phosphatide that under normal condition, prepares.
At CO
2Prepare in the highly acetylated soybean phospholipid supercritical CO under the supercritical state
2Fluid is playing an important role aspect the purifying high-purity soybean phospholipid, is beneficial to the raising of phosphatidylcholine content, finally obtains the acidylate rate and be 93.2% highly acetylated soybean phospholipid, the highly acetylated phosphatide for preparing under the normal condition.
Embodiment
Below further describe the present invention by specific embodiment; but these embodiment only are illustrative; protection scope of the present invention is not consisted of any impact; it will be understood by those skilled in the art that any modification that spirit according to the present invention is made and replace and all fall within the scope of protection of the present invention.
Embodiment one: the step of present embodiment is as follows:
Step 1: at CO
2Under the supercritical state, with transparent phosphatide and with diacetyl oxide heat altogether in autoclave, selecting the consumption of diacetyl oxide is 1.2%～5.2% of transparent phosphatide quality, at temperature 60 C, stirring velocity is to stir 35min under the condition of 30rpm.After reaction for some time, add phosphatide raw material weight 2%, concentration is 10% sodium hydroxide neutralization, adjust pH is 7.Then below the vacuum hydro-extraction to 1%, be cooled to rapidly 50 ℃, obtain highly acetylated soybean phospholipid, measure its acidylate rate, determine the consumption of diacetyl oxide.
Step 2: the selective reaction temperature is 35～85 ℃, and the same step 1 of process is determined the reaction optimum temperuture;
Step 3: the selective reaction time is respectively 20～45min, and the same step 1 of process is determined the reaction times;
Step 4: the pH of selective reaction is 6.5～8.5, and the same step 1 of process is determined the pH that reacts;
Specific implementation method two: the diacetyl oxide consumption during this implementation method is will react in the step 1 with specific implementation method one difference is 1.2%～4.4% of transparent phosphatide quality, and other composition is identical with specific implementation method one with step;
Specific implementation method three: the diacetyl oxide consumption during this implementation method is will react in the step 1 with specific implementation method one difference is 2%～3.6% of transparent phosphatide quality, and other composition is identical with specific implementation method one with step;
Specific implementation method four: it is 35～75 ℃ that this implementation method and specific implementation method one difference are in the step 2 temperature of reaction, and other composition is identical with specific implementation method one with step;
Specific implementation method five: it is 45～75 ℃ that this implementation method and specific implementation method one difference are in the step 2 temperature of reaction, and other composition is identical with specific implementation method one with step;
Specific implementation method six: this implementation method is in the step 3 to be 20～40min in the reaction times with specific implementation method one difference, and other composition is identical with specific implementation method one with step;
Specific implementation method seven: this implementation method is in the step 3 to be 25～40min in the reaction times with specific implementation method one difference, and other composition is identical with specific implementation method one with step;
Specific implementation method eight: this implementation method and specific implementation method one difference are in the step 4 that the pH with reaction response is 6.9～8.1, and other composition is identical with specific implementation method one with step;
Specific implementation method nine: this implementation method and specific implementation method one difference are in the step 4 that the pH with reaction response is 6.9～7.7, and other composition is identical with specific implementation method one with step;
Claims (9)
1. one kind at CO
2The method of the highly acetylated soybean phospholipid of preparation under the supercritical state, the method for under certain reaction conditions, carrying out highly acetylated soybean phospholipid preparation, its characterization step is as follows:
Step 1: at CO
2Under the supercritical state, with transparent phosphatide and with diacetyl oxide heat altogether in autoclave, selecting the consumption of diacetyl oxide is 1.2%～5.2% of transparent phosphatide quality, at temperature 60 C, stirring velocity is to stir 35min under the condition of 30rpm.After reaction for some time, add phosphatide raw material weight 2%, concentration is 10% sodium hydroxide neutralization, adjust pH is 7.Then below the vacuum hydro-extraction to 1%, be cooled to rapidly 50 ℃, obtain highly acetylated soybean phospholipid, measure its acidylate rate, determine the consumption of diacetyl oxide.
Step 2: the selective reaction temperature is 35～85 ℃, and the same step 1 of process is determined the reaction optimum temperuture;
Step 3: the selective reaction time is respectively 20～45min, and the same step 1 of process is determined the reaction times;
Step 4: the pH of selective reaction is 6.5～8.5, and the same step 1 of process is determined the pH that reacts;
2. according to claim 1 a kind of at CO
2The method of the highly acetylated soybean phospholipid of preparation under the supercritical state, the method for under certain reaction conditions, carrying out highly acetylated soybean phospholipid preparation, the diacetyl oxide consumption in it is characterized in that will reacting in the step 1 is 1.2%～4.4% of transparent phosphatide quality.
3. according to claim 1 a kind of at CO
2The method of the highly acetylated soybean phospholipid of preparation under the supercritical state, the method for under certain reaction conditions, carrying out highly acetylated soybean phospholipid preparation, the diacetyl oxide consumption in it is characterized in that will reacting in the step 1 is 2%～3.6% of transparent phosphatide quality.
4. according to claim 1 a kind of at CO
2The method of the highly acetylated soybean phospholipid of preparation under the supercritical state, the method for carrying out highly acetylated soybean phospholipid preparation under certain reaction conditions is characterized in that the selective reaction temperature is 35～75 ℃ in the step 2.
5. according to claim 1 a kind of at CO
2The method of the highly acetylated soybean phospholipid of preparation under the supercritical state, the method for carrying out highly acetylated soybean phospholipid preparation under certain reaction conditions is characterized in that the selective reaction temperature is 45～75 ℃ in the step 2.
6. according to claim 1 a kind of at CO
2The method of the highly acetylated soybean phospholipid of preparation under the supercritical state, the method for carrying out highly acetylated soybean phospholipid preparation under certain reaction conditions is characterized in that the selective reaction time is respectively 20～40min in the step 3.
7. according to claim 1 a kind of at CO
2The method of the highly acetylated soybean phospholipid of preparation under the supercritical state, the method for carrying out highly acetylated soybean phospholipid preparation under certain reaction conditions is characterized in that the selective reaction time is respectively 25～40min in the step 3.
8. according to claim 1 a kind of at CO
2The method of the highly acetylated soybean phospholipid of preparation under the supercritical state, the method for under certain reaction conditions, carrying out highly acetylated soybean phospholipid preparation, the pH that it is characterized in that selective reaction in the step 4 is 6.9～8.1.
9. according to claim 1 a kind of at CO
2The method of the highly acetylated soybean phospholipid of preparation under the supercritical state, the method for under certain reaction conditions, carrying out highly acetylated soybean phospholipid preparation, the pH that it is characterized in that selective reaction in the step 4 is 6.9～7.7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110278485.7A CN103012467B (en) | 2011-09-20 | 2011-09-20 | A kind of at CO 2the method of highly acetylated soybean phospholipid is prepared under supercritical state |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110278485.7A CN103012467B (en) | 2011-09-20 | 2011-09-20 | A kind of at CO 2the method of highly acetylated soybean phospholipid is prepared under supercritical state |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103012467A true CN103012467A (en) | 2013-04-03 |
| CN103012467B CN103012467B (en) | 2015-12-16 |
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| CN201110278485.7A Active CN103012467B (en) | 2011-09-20 | 2011-09-20 | A kind of at CO 2the method of highly acetylated soybean phospholipid is prepared under supercritical state |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035436C (en) * | 1994-03-07 | 1997-07-16 | 中国科学院山西煤炭化学研究所 | Method for extracting high-purity lecithin with supercritical CO2 |
| EP1004245A2 (en) * | 1998-11-27 | 2000-05-31 | Krupp Uhde GmbH | Process for recovering in particular lecithin from dried egg |
| US20030072716A1 (en) * | 2001-06-22 | 2003-04-17 | Raveendran Poovathinthodiyil | Renewable, carbohydrate based CO2-philes |
| CN1634939A (en) * | 2003-12-29 | 2005-07-06 | 黑龙江省大豆技术开发研究中心 | Supercritical CO2 extraction process for soya bean lecithin |
| CN1687084A (en) * | 2005-04-30 | 2005-10-26 | 海城后英生物工程有限公司 | Technique for producing soya bean lecithin |
| CN101423530A (en) * | 2007-10-30 | 2009-05-06 | 东北农业大学 | Soya bean lecithin hydrogenization method using supercritical CO2 as dissolving agent |
-
2011
- 2011-09-20 CN CN201110278485.7A patent/CN103012467B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035436C (en) * | 1994-03-07 | 1997-07-16 | 中国科学院山西煤炭化学研究所 | Method for extracting high-purity lecithin with supercritical CO2 |
| EP1004245A2 (en) * | 1998-11-27 | 2000-05-31 | Krupp Uhde GmbH | Process for recovering in particular lecithin from dried egg |
| US20030072716A1 (en) * | 2001-06-22 | 2003-04-17 | Raveendran Poovathinthodiyil | Renewable, carbohydrate based CO2-philes |
| CN1634939A (en) * | 2003-12-29 | 2005-07-06 | 黑龙江省大豆技术开发研究中心 | Supercritical CO2 extraction process for soya bean lecithin |
| CN1687084A (en) * | 2005-04-30 | 2005-10-26 | 海城后英生物工程有限公司 | Technique for producing soya bean lecithin |
| CN101423530A (en) * | 2007-10-30 | 2009-05-06 | 东北农业大学 | Soya bean lecithin hydrogenization method using supercritical CO2 as dissolving agent |
Non-Patent Citations (4)
| Title |
|---|
| 廖传华等: "《超临界流体萃取技术》", 31 July 2004, 化学工业出版社 * |
| 徐振山等: "大豆磷脂改性及其改性技术分析", 《粮食与油脂》 * |
| 潘丽等: ""磷脂改性方法的研究进展(Ⅰ)-物理与化学改性"", 《中国油脂》 * |
| 王利等: "大豆磷脂的改性方法及其应用", 《黑龙江八一农垦大学学报》 * |
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| CN103012467B (en) | 2015-12-16 |
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Effective date of registration: 20170830 Address after: Xiangfang District of Heilongjiang city of Harbin province haping road 150001 No. 1 Patentee after: The 93 group Harbin Wellcome Food Co. Ltd. Address before: 150030, room 6, building 104, 3 Bei'an street, Daoli District, Heilongjiang, Harbin Patentee before: Yu Dianyu |
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Address after: 150001 No.1, haping East Road, Xiangfang District, Harbin City, Heilongjiang Province Patentee after: Jiusan Food Co.,Ltd. Address before: 150001 No.1, haping East Road, Xiangfang District, Harbin City, Heilongjiang Province Patentee before: THE NINE THREE GROUP HARBIN WELLCOME FOOD Co.,Ltd. |