CN101423530B - Soya bean lecithin hydrogenization method using supercritical CO2 as dissolving agent - Google Patents
Soya bean lecithin hydrogenization method using supercritical CO2 as dissolving agent Download PDFInfo
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- CN101423530B CN101423530B CN2007101445182A CN200710144518A CN101423530B CN 101423530 B CN101423530 B CN 101423530B CN 2007101445182 A CN2007101445182 A CN 2007101445182A CN 200710144518 A CN200710144518 A CN 200710144518A CN 101423530 B CN101423530 B CN 101423530B
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- steel autoclave
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Abstract
The invention provides a method for hydrogenating soybean lecithin with supercritical CO2 as solvent. The invention relates to a reaction method for the hydrogenation of soybean lecithin. The method solves the problems that in the prior hydrogenation method, an isomerization reaction is easy to happen so as to generate anti-form fatty acid ester; and the prior method has harmful solvent residue. The method comprises the following steps: adding a lecithin sample into a kettle, adding a certain amount of catalyzer and beads into the kettle, and then carrying out a leakage test; charging CO2 into the kettle, then charging H2 into the kettle to reach the pressure of 12 to 14 MPa when a supercritical stage is reached; and heating up the kettle, cooling down the kettle to a room temperature when the reaction is completed, dissolving the reactant, and obtaining the product after centrifugal separation and rotary evaporation. The method adopts the supercritical CO2 fluid as the solvent to carry out the hydrogenation reaction. As H2 can be mixed and dissolved with the supercritical CO2, the mass transfer resistance from a gas phase to a supercritical phase is reduced, thereby increasing the hydrogenation stability of the hydrogenated lecithin, improving the performance of the lecithin, and widening the application range of the lecithin. No harmful solvent is added during the whole process of hydrogenation, thereby avoiding the problem of the harmful solvent residue.
Description
Technical field
The present invention relates to a kind of reaction method of soybean phospholipid hydrogenation.
Background technology
Phosphatide is prevalent in the protoplasma and cytolemma of animal and plant cells as a kind of basic substance of life.Purified phosphatide is white waxy solid, at low temperatures easily crystallization, water-swelling.Because lipid acid contains more unsaturated double-bond in the natural phospholipid molecule, thereby very unstable, easy oxidative rancidity in air makes to darken and produce bad smell, has limited the application of phosphatide in makeup, foodstuff additive and pharmaceutical industries.At present the soybean phospholipid product exist color and luster dark, peculiar smell, product instability, easy shortcomings such as oxidation are arranged, need carry out could in wider field, using after the modification to it.The method of modification has hydrolysis, sulfonation, hydroxylation, acidylate, hydrogenation and compounded technology etc., but these method of modifying just can reach perfect condition after need adding many chemical reagent, and dissolvent residual is more, therefore is badly in need of a kind of new modified method of invention.This invention is not to use chemical reagent as solvating agent, but with CO
2For solvent carries out hydrogenation reaction, speed of response is fast, does not produce the time of isomer, can produce the wider hydrogenated phospholipid product of range of application.
Hydrogenation is one of phospholipid modified method, original hydrogenation mechanism is in solid-liquid-gas three-phase system, hydrogen is diffused into the catalyst surface place in three-phase system, adsorbed by catalyst active center, form surface adsorption attitude hydrogen, the unsaturated fatty acids chain of forming phosphatide runs into ADSORPTION STATE hydrogen, hydrogenation takes place, thereby obtain the hydrogenation product.In the addition reaction process of system, H
2Feed speed is slow excessively, and a small amount of phospholipid molecule is adsorbed by the catalyst activation center, forms ADSORPTION STATE phosphatide.ADSORPTION STATE phosphatide and activated state hydrogen meet, and isomerization reaction easily takes place, and the lipid acid in the phosphatide easily generates trans fatty acid fat.And this reaction is by chemical agent dissolves phosphatide, carry out hydrogenation again, after hydrogenation finishes, with rotary evaporation solvent is steamed, but can not all evaporating, removes by the chemical reagent that is used to dissolve phosphatide, thereby the residual of trace arranged, and it is unfavorable to take human body for a long time, and this product can not be applied in the pharmaceutical industries.
Summary of the invention
Isomerization reaction easily takes place in order to solve in the present invention in the existing method for hydrogenation, generate the problem of trans fatty acid fat, and the drawback of residual harmful substance, and has proposed a kind of supercritical CO of using
2Method for the solvating agent hydrogenated soya phosphatide.
Step of the present invention is as follows:
Step 1: the processing before the reaction: in stainless steel autoclave, add 5g soybean phospholipid sample, add 3%～7% Pd/C catalyzer of soybean phospholipid simultaneously, add again and stir magnetic bead;
Step 2: leak test: the CO that in stainless steel autoclave, injects 3～5MPa
2Gas carries out leak test;
Step 3: substitution gas: use CO
2Air in the displacement stainless steel autoclave 3～5 times, its pressure is less than 4MPa;
Step 4: fill CO
2: in stainless steel autoclave, charge into CO
2Gas, pressure is 7～9MPa, makes it be in supercritical state under temperature of reaction;
Step 5: fill H
2: in stainless steel autoclave, charge into H again
2, total pressure is 12～14MPa;
Step 6: secondary leak test: the stainless steel autoclave that will charge into gas carries out the secondary leak test;
Step 7: heating: adopt well heater that stainless steel autoclave is heated, Heating temperature rises to 120～140 ℃, and be 1.5～2h heat-up time;
Step 8: react: start magnetic agitation under the condition of constant temperature and pressure, mixing speed is 50～80 rev/mins, and the reaction times is 2～3h;
Step 9: reaction finishes: reaction makes stainless steel autoclave be cooled to room temperature after finishing, and temperature fall time is 1.5～2h, emits gas, opens stainless steel autoclave, adds dehydrated alcohol, with the product dissolving, takes out reaction product;
Step 10: reacted processing: adopt separating centrifuge to remove the Pd/C catalyzer, rotary evaporation is removed dehydrated alcohol then, reduces to room temperature, obtains final product.
Solvating agent among the present invention is a supercritical CO
2Fluid, CO
2Under certain temperature more than the stagnation point and the pressure be fluid between gas and liquid.Its fluid behavior is similar to gas, because H
2Energy and supercritical CO
2Fluid is miscible, has weakened the resistance to mass transfer from the gas phase to the supercritical phase, and just solid-liquid-gas three-phase body is at supercritical CO
2In the system, make H
2At supercritical CO
2Diffusion dissolution in the system, hydrogen dissolving velocity of diffusion is accelerated H
2The feed rate abundance, become activated state hydrogen by catalyst active center's activation, thereby form activated state hydrogen fast, be difficult for taking place isomerization reaction, with the unsaturated fatty acids chain of forming phosphatide hydrogenation taking place respectively, just becomes diolefinic acid fat after the hydrogenation of trienic acid fat; Diolefinic acid fat (comprising newly-generated) hydrogenation simultaneously becomes monoenoic acid fat, becomes saturated acid fat after monoenoic acid fat (the comprising newly-generated) hydrogenation, and the time of reaction is shortened.In whole hydrogenation process, do not have hazardous solvent to add, thereby avoided the residual problem of hazardous solvent.The present invention is improved the phosphatide stable hydride after the hydrogenation, improves its oxidation-resistance, widens its Application Areas, can be used for kephalin, powder lecithin, Yelkin TTS-70, Yelkin TTS-90 etc.Adopting method of the present invention to carry out the hydrogenation iodine number is 90～95 soybean lecithin, and the iodine number that finally obtains hydrogenated soy phosphatidyl choline is 40～50.
Embodiment
Embodiment one: the step of present embodiment is as follows:
Step 1: the processing before the reaction: in stainless steel autoclave, add 5g phosphatide sample, add 3%～7% Pd/C catalyzer of phosphatide simultaneously, add again and stir magnetic bead;
Step 2: leak test: the CO that in stainless steel autoclave, injects 3～5MPa
2Gas carries out leak test;
Step 3: substitution gas: use CO
2Air in the displacement stainless steel autoclave 3～5 times, its pressure is less than 4MPa;
Step 4: fill CO
2: in stainless steel autoclave, charge into CO
2Gas, pressure is 7～9MPa, makes it be in supercritical state under temperature of reaction;
Step 5: fill H
2: in stainless steel autoclave, charge into H again
2, total pressure is 12～14MPa;
Step 6: secondary leak test: the stainless steel autoclave that will charge into gas carries out the secondary leak test;
Step 7: heating: adopt well heater that stainless steel autoclave is heated, Heating temperature rises to 120～140 ℃, and be 1.5～2h heat-up time;
Step 8: react: start magnetic agitation under the condition of constant temperature and pressure, mixing speed is 50～80 rev/mins, and the reaction times is 2～3h;
Step 9: reaction finishes: reaction makes stainless steel autoclave be cooled to room temperature after finishing, and temperature fall time is 1.5～2h, emits gas, opens stainless steel autoclave, adds dehydrated alcohol, with the product dissolving, takes out reaction product;
Step 10: reacted processing: adopt separating centrifuge to remove the Pd/C catalyzer, rotary evaporation is removed dehydrated alcohol then, reduces to room temperature, obtains final product.
The equipment that adopts in the present embodiment is: DF-101s heat collecting type thermostatically heating magnetic stirring apparatus, LD4-2A low speed centrifuge, 150mL autoclave, Rotary Evaporators.
Embodiment two: present embodiment and embodiment one difference are that the Pd/C catalyzer contains 5% Pd, and other composition is identical with embodiment one with step.
Embodiment three: present embodiment and embodiment one difference are to charge in the step 4 CO
2The pressure of gas is 7.5～8.5MPa.Other composition is identical with embodiment one with step.
Embodiment four: present embodiment and embodiment one difference are to charge in the step 4 CO
2The pressure of gas is 8MPa.Other composition is identical with embodiment one with step.
Embodiment five: present embodiment and embodiment one difference are CO in the step 5
2And H
2Total pressure be 12.5～13.5MPa.Other composition is identical with embodiment one with step.
Embodiment six: present embodiment and embodiment one difference are CO in the step 5
2And H
2Total pressure be 13MPa.Other composition is identical with embodiment one with step.
Embodiment seven: present embodiment and embodiment one difference are that the Heating temperature in the step 7 rises to 120～140 ℃, and be 2h heat-up time.Other composition is identical with embodiment one with step.
Embodiment eight: present embodiment and embodiment one difference are that the Heating temperature in the step 7 rises to 135 ℃, and be 1.5h heat-up time.Other composition is identical with embodiment one with step.
Embodiment nine: present embodiment and embodiment one difference are the reaction times 2.2～2.8h in the step 8.Other composition is identical with embodiment one with step.
Embodiment ten: present embodiment and embodiment one difference are the reaction times 2.5h in the step 8.Other composition is identical with embodiment one with step.
Claims (10)
1. use supercritical CO for one kind
2Be the method for solvating agent hydrogenated soya phosphatide, it is characterized in that its step is as follows:
Step 1: the processing before the reaction: in stainless steel autoclave, add 5g soybean phospholipid sample, add 3%～7% Pd/C catalyzer of soybean phospholipid simultaneously, add again and stir magnetic bead;
Step 2: leak test: the CO that in stainless steel autoclave, injects 3～5MPa
2Gas carries out leak test;
Step 3: substitution gas: use CO
2Air in the displacement stainless steel autoclave 3～5 times, its pressure is less than 4MPa;
Step 4: fill CO
2: in stainless steel autoclave, charge into CO
2Gas, pressure is 7～9MPa, makes it be in supercritical state under temperature of reaction;
Step 5: fill H
2: in stainless steel autoclave, charge into H again
2, total pressure is 12～14MPa;
Step 6: secondary leak test: the stainless steel autoclave that will charge into gas carries out the secondary leak test;
Step 7: heating: adopt well heater that stainless steel autoclave is heated, Heating temperature rises to 120～140 ℃, and be 1.5～2h heat-up time;
Step 8: react: start magnetic agitation under the condition of constant temperature and pressure, mixing speed is 50～80 rev/mins, and the reaction times is 2～3h;
Step 9: reaction finishes: reaction makes stainless steel autoclave be cooled to room temperature after finishing, and temperature fall time is 1.5～2h, emits gas, opens stainless steel autoclave, adds dehydrated alcohol, with the product dissolving, takes out reaction product;
Step 10: reacted processing: adopt separating centrifuge to remove the Pd/C catalyzer, rotary evaporation is removed dehydrated alcohol then, reduces to room temperature, obtains final product.
2. a kind of supercritical CO of using according to claim 1
2Be the method for solvating agent hydrogenated soya phosphatide, it is characterized in that the Pd/C catalyzer contains 5% Pd.
3. a kind of supercritical CO of using according to claim 1
2Be the method for solvating agent hydrogenated soya phosphatide, it is characterized in that charging in the step 4 CO
2The pressure of gas is 7～9MPa.
4. a kind of supercritical CO of using according to claim 1
2Be the method for solvating agent hydrogenated soya phosphatide, it is characterized in that charging in the step 4 CO
2The pressure of gas is 8MPa.
5. a kind of supercritical CO of using according to claim 1
2Be the method for solvating agent hydrogenated soya phosphatide, it is characterized in that CO in the step 5
2And H
2Total pressure be 12～14MPa.
6. a kind of supercritical CO of using according to claim 1
2Be the method for solvating agent hydrogenated soya phosphatide, it is characterized in that CO in the step 5
2And H
2Total pressure be 13MPa.
7. a kind of supercritical CO of using according to claim 1
2Be the method for solvating agent hydrogenated soya phosphatide, it is characterized in that the Heating temperature in the step 7 rises to 125 ℃～135 ℃, be 2h heat-up time.
8. a kind of supercritical CO of using according to claim 1
2Be the method for solvating agent hydrogenated soya phosphatide, it is characterized in that the Heating temperature in the step 7 rises to 135 ℃, be 1.5h heat-up time.
9. a kind of supercritical CO of using according to claim 1
2Be the method for solvating agent hydrogenated soya phosphatide, it is characterized in that the reaction times 2.2～2.8h in the step 8.
10. a kind of supercritical CO of using according to claim 1
2Be the method for solvating agent hydrogenated soya phosphatide, it is characterized in that the reaction times 2.5h in the step 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101445182A CN101423530B (en) | 2007-10-30 | 2007-10-30 | Soya bean lecithin hydrogenization method using supercritical CO2 as dissolving agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101445182A CN101423530B (en) | 2007-10-30 | 2007-10-30 | Soya bean lecithin hydrogenization method using supercritical CO2 as dissolving agent |
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|---|---|
| CN101423530A CN101423530A (en) | 2009-05-06 |
| CN101423530B true CN101423530B (en) | 2011-01-19 |
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|---|---|---|---|
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798548A (en) * | 2010-04-08 | 2010-08-11 | 东北农业大学 | Method for developing lube base oil with hydrogenated soybean oil under supercritical CO2 state |
| CN103012467B (en) * | 2011-09-20 | 2015-12-16 | 于殿宇 | A kind of at CO 2the method of highly acetylated soybean phospholipid is prepared under supercritical state |
| CN108822146A (en) * | 2018-06-29 | 2018-11-16 | 中国药科大学 | The production method of high-purity hydrogenated soy phosphatidyl choline |
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Non-Patent Citations (3)
| Title |
|---|
| 张玉军.磷脂的化学改性与生物改性技术.《日用化学工业》.2003,第33卷(第3期),第167-169和178页. * |
| 金希江.氢化大豆磷脂的研制.《精细化工》.1999,第16卷(第6期),第5-6页. * |
| 高海春 等.超临界CO2下Pd/C催化剂催化松香加氢反应的研究.《生物质化学工程》.2006,第40卷(第3期),第13-16页. * |
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Inventor after: Jiang Lianzhou Inventor after: Sun Bo Inventor after: Chang Yunhe Inventor after: Wang Yan Inventor after: Wang Liqi Inventor after: Hu Lizhi Inventor after: Yu Dianyu Inventor after: Zhu Xiuqing Inventor after: Zhang Zhi Inventor after: Wang Jin Inventor after: Liu Jing Inventor after: Zhou Xiaodan Inventor before: Yu Dianyu Inventor before: Jiang Lianzhou Inventor before: Song Yuqing Inventor before: Zhu Xiuqing Inventor before: Zhang Zhi Inventor before: Wang Jin Inventor before: Zhang Xiuling |
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Free format text: CORRECT: INVENTOR; FROM: YU DIANYU JIANG LIANZHOU SONG YUQING ZHU XIUQING ZHANG ZHI WANG JIN ZHANG XIULING TO: JIANG LIANZHOU WANG LIQI HU LIZHI YU DIANYU ZHU XIUQING ZHANG ZHI WANG JIN LIU JING ZHOU XIAODAN SUN BO CHANG YUNHE WANG YAN |
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Granted publication date: 20110119 Termination date: 20131030 |