CN112125798A - Erucic acid purification method suitable for industrial amplification production - Google Patents
Erucic acid purification method suitable for industrial amplification production Download PDFInfo
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- CN112125798A CN112125798A CN202011025604.3A CN202011025604A CN112125798A CN 112125798 A CN112125798 A CN 112125798A CN 202011025604 A CN202011025604 A CN 202011025604A CN 112125798 A CN112125798 A CN 112125798A
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- erucic acid
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Abstract
The invention provides an erucic acid purification method suitable for industrial amplification production, which comprises the following steps: dissolving the erucic acid crude product in a solvent to obtain an erucic acid crude product sample solution; loading the erucic acid crude product loading liquid into an erucic acid preparation column; the filler in the erucic acid preparation column takes silica gel as a matrix, and octadecylsilane and divinylbenzene are bonded on the silica gel; eluting the erucic acid preparation column with the eluent, collecting the elution components, merging the qualified eluents, and concentrating to obtain the purified erucic acid. The invention adopts the purification method to purify the erucic acid, has simple operation and is suitable for large-scale production. The invention provides a low-energy consumption erucic acid purification method from the aspect of chromatographic purification, and pilot test verifies that the method provides a basis for the feasibility of the erucic acid. The experimental results show that: the purity of the purified erucic acid is higher than 95 percent, and the yield is higher than 86 percent.
Description
Technical Field
The invention belongs to the technical field of purification, and particularly relates to an erucic acid purification method suitable for industrial amplification production.
Background
Erucic acid, cis-13-docosenoic acid, molecular formula: c22H42O2. Erucic acid is a soft solid monounsaturated fatty acid, is white needle-shaped crystal at normal temperature, is very easy to dissolve in ether, ethanol and methanol and is not soluble in water. Erucic acid is mainly used for producing erucamide, and can also be used for preparing various surfactants, cosmetics, chemical fiber oil solutions and the like. Erucic acid is present in great amounts in oil such as rape oil, crambe oil, mustard oil and the like in the form of glyceric acid. Erucic acidThe molecular carbon chain is longer than that of oleic acid and linolenic acid, and has stronger hydrophobicity, waterproofness and excellent lubricity. Erucic acid per se oxidizes and polymerizes much slower than those with short carbon chains. The derivatives thereof are used in many fields such as antistatic agents, lubricants, plasticizers, light and heat stabilizers, antiblocking agents, synthetic resins (nylon 1313), synthetic perfumes, etc. Erucic acid plays a significant role in various modern industrial fields by virtue of the advantages of wide application, high added value, large market demand, reproducibility and the like, and is known as an important fine chemical raw material in the 21 st century.
Most of the erucic acid purification adopts a rectification method, the process is complex, and the energy consumption is large.
Disclosure of Invention
In view of the above, the present invention aims to provide an erucic acid purification method suitable for industrial scale-up production, which is simple and can be used for scale-up production.
The invention provides an erucic acid purification method suitable for industrial amplification production, which comprises the following steps:
dissolving the erucic acid crude product in a solvent to obtain an erucic acid crude product sample solution;
loading the erucic acid crude product loading liquid into an erucic acid preparation column; the filler in the erucic acid preparation column takes silica gel as a matrix, and octadecylsilane and divinylbenzene are bonded on the silica gel;
eluting the erucic acid preparation column with the eluent, collecting the elution components, merging the qualified eluents, and concentrating to obtain the purified erucic acid.
Preferably, the solvent is a mixed solution of an organic solvent and water in a volume ratio of 0-20: 08-100;
the organic solvent is selected from one or more of methanol, ethanol and acetonitrile.
Preferably, the mass ratio of the octadecylsilane to the divinylbenzene is 1-10: 1.
Preferably, the eluent is a mixed solution of an organic solvent and water in a volume ratio of 0-20: 80-100;
the organic solvent is selected from one or more of methanol, ethanol and acetonitrile.
Preferably, the purity of erucic acid in the qualified eluate is higher than 95%.
Preferably, the content of erucic acid in the erucic acid crude product is 35-75%; the concentration of the erucic acid crude product loading liquid is 50-100 mg/ml; the loading does not exceed 10%.
Preferably, the flow rate of the sample loading is 10-400 ml/min; the flow rate of elution is 10-400 ml/min.
The invention provides an erucic acid purification method suitable for industrial amplification production, which comprises the following steps: dissolving the erucic acid crude product in a solvent to obtain an erucic acid crude product sample solution; loading the erucic acid crude product loading liquid into an erucic acid preparation column; the filler in the erucic acid preparation column takes silica gel as a matrix, and octadecylsilane and divinylbenzene are bonded on the silica gel; eluting the erucic acid preparation column with the eluent, collecting the elution components, merging the qualified eluents, and concentrating to obtain the purified erucic acid. The invention adopts the purification method to purify the erucic acid, has simple operation and is suitable for large-scale production. The invention provides a low-energy consumption erucic acid purification method from the aspect of chromatographic purification, and pilot test verifies that the method provides a basis for the feasibility of the erucic acid. The experimental results show that: the purity of the purified erucic acid is higher than 95 percent, and the yield is higher than 86 percent.
Drawings
FIG. 1 is a liquid chromatogram of the crude erucic acid purification process provided in example 1 of the present invention.
Detailed Description
The invention provides an erucic acid purification method suitable for industrial amplification production, which comprises the following steps:
dissolving the erucic acid crude product in a solvent to obtain an erucic acid crude product sample solution;
loading the erucic acid crude product loading liquid into an erucic acid preparation column; the filler in the erucic acid preparation column takes silica gel as a matrix, and octadecylsilane and divinylbenzene are bonded on the silica gel;
eluting the erucic acid preparation column with the eluent, collecting the elution components, merging the qualified eluents, and concentrating to obtain the purified erucic acid.
In the invention, the mass content of erucic acid in the erucic acid crude product is 35-75%; in the specific embodiment, the content of erucic acid in the erucic acid crude product is 65.87%.
The solvent is a mixed solution of an organic solvent and water in a volume ratio of 0-20: 80-100; the organic solvent is selected from one or more of methanol, ethanol and acetonitrile. In a specific embodiment, the solvent is a mixed solution of water and methanol in a volume ratio of 8: 92; or a mixture of water and acetonitrile in a volume ratio of 12: 88; or a mixture of water and methanol in a volume ratio of 10: 90. The concentration of the erucic acid crude product loading liquid is 50-100 mg/ml; in a specific embodiment, the concentration of the crude erucic acid sample solution is 100 mg/ml.
The invention loads the erucic acid crude product loading liquid into an erucic acid preparation column; the filler in the erucic acid preparation column takes silica gel as a matrix, and octadecylsilane and divinylbenzene are bonded on the silica gel. In the invention, the mass ratio of octadecylsilane to divinylbenzene is 1-10: 1; the octadecyl silane and the divinylbenzene account for 15 to 19 percent of the mass of the silica gel. The loading capacity of the sample loading is not more than 10%, and preferably 4-8%. The flow rate of the sample loading is 10-400 ml/min; in particular embodiments, the flow rate of the sample is 200ml/min, or 400 ml/min.
The invention adopts eluent to elute the erucic acid preparation column which is completely loaded with the sample, collects elution components, combines qualified eluent, and obtains purified erucic acid after concentration. The eluent is a mixed solution of an organic solvent and water in a volume ratio of 0-20: 80-100; the organic solvent in the eluent is preferably selected from one or more of methanol, ethanol and acetonitrile. In the invention, the eluent is a mixed solution of water and methanol in a volume ratio of 8: 92; or a mixture of water and acetonitrile in a volume ratio of 12: 88; or a mixture of water and methanol in a volume ratio of 10: 90. The flow rate of elution is 10-400 ml/min; in a specific embodiment, the flow rate of the elution is 400 ml/min.
In the present invention, the erucic acid content in the qualified eluent is higher than 95%.
To further illustrate the present invention, the following examples are provided to describe in detail the method for purifying erucic acid suitable for industrial scale-up production, but they should not be construed as limiting the scope of the present invention.
1. Instruments and materials
The method comprises the following steps of preparing a erucic acid crude product, a liquid chromatograph LC6000 for Sepax, one analytical balance (hundredth), one analytical balance (ten thousand), a volumetric flask (10ml), 1ml of a pipette, 200 mu L of a pipette (matching with a pipette head), one magnetic stirrer, a vortex mixer, a measuring cylinder (500ml and 100ml), a disposable dropper, 5ml of centrifuge tube, 2L of conical bottles, preservative films, marking pens, label paper and the like;
2. reagent
Methanol (analytical grade), acetonitrile (analytical grade), ethanol (analytical grade), purified water, etc
3. The experimental steps are as follows:
(1) weighing a sample: weighing a crude erucic acid product on an analytical balance;
(2) solvent preparation: preparing a proper amount of organic solvent-water mixed solution;
(3) sample dissolution: taking a proper amount of the solvent prepared in the step (2), adding the solvent into the erucic acid crude product in the step (1), sealing the erucic acid crude product with a preservative film, adding a stirrer, keeping the stirring state on a magnetic stirrer to fully mix the erucic acid crude product with the preservative film, then fixing the volume, and uniformly mixing the solution for later use;
(4) and (3) chromatographic column balancing: on an LC6000 instrument, under the condition of switching on an erucic acid preparation column, washing the equilibrium column by eluent, and balancing;
(5) sample loading: stopping all pumps after the step (4) is finished, inserting pipelines into the prepared solvent in the step (2), flushing the pipelines, stopping the pumps, replacing the pipelines into the prepared erucic acid crude product, stopping the pumps after the sample loading is finished, replacing the pipelines into the residual solvent in the step (2), and stopping the pumps after the flushing;
(6) sample elution: after the step 5 is finished, the pump pipeline is changed into the eluent, and meanwhile, the online signal record of the preparation workstation is started to start elution;
(7) collecting samples: samples were collected starting when the appearance of the target peak was seen, every 2 min.
See the sample preparation map in detail;
(8) collecting the analysis and detection of the sample and combining qualified samples.
Example 1
Column for chromatography, erucic acid preparation column (100mm × 250 mm);
eluent, water: methanol-8: 92;
the flow rate is 400ml/min sample volume, 400ml column temperature and room temperature;
the sample is 100mg/ml under the pressure of 1.1 MPa;
the instrument is that Sepax prepares chromatograph LC 6000;
the detection wavelength is UV @214 nm;
the specific method comprises the following steps:
1. weighing a sample: weighing 40g of erucic acid crude product on an analytical balance;
2. preparing a solvent: preparing a proper amount of 92% methanol aqueous solution for later use;
3. sample dissolution: taking a proper amount of the solvent prepared in the step 2, adding the solvent into 40g of erucic acid crude product, sealing the erucic acid crude product with a preservative film, adding a stirrer, keeping the stirring state on a magnetic stirrer, fully mixing the mixture, fixing the volume to 400ml, and uniformly mixing the mixture for later use;
4. and (3) chromatographic column balancing: on an LC6000 instrument, under the condition of switching on an erucic acid preparation column, washing the equilibrium column by eluent at the flow rate of 400ml/min, and balancing for 15 min;
5. sample loading: stopping all pumps after the step 4 is finished, replacing pipelines into the prepared erucic acid crude product, loading the erucic acid crude product at the speed of 400ml/min for 1min, and stopping the pumps;
6. sample elution: after the step 5 is finished, the pump pipeline is changed into the eluent, the on-line signal record of the preparation workstation is started at the same time, and the elution is started under the condition of 400 ml/min;
7. collecting samples: the sample collection was started when the appearance of the target peak was seen. As shown in figure 1, collecting the components with the retention time of 14-32 min;
8. collecting samples for analysis and detection and combining qualified samples;
9. data during purification are shown in table 1:
table 1 statistics of data before and after purification of example 1
| Quality (g) | Purity (%) | Recovery (%) | |
| Crude product | 40.00 | 65.87 | -- |
| Purified sample | 35.29 | 95.72 | 88.23 |
Example 2
Taking 40g of crude erucic acid with the content of 65.87% (m/m), adding water: acetonitrile 12:88(V/V)400ml, stirring to fully dissolve; loading to an erucic acid chromatographic column (100mm × 250mm, containing about 0.98kg of filler) balanced by eluent (water: acetonitrile: 12:88), loading at a flow rate of 200ml/min, eluting with eluent (water: acetonitrile: 12:88) at a flow rate of 400ml/min for 60min, collecting erucic acid component solution by HPLC detection, mixing qualified components, and concentrating to obtain pure erucic acid product 34.57g with a purity of 95.71% and a recovery rate of 86.43%.
Example 3
Taking 40g of crude erucic acid with the content of 65.87% (m/m), adding water: ethanol (10: 90 (V/V)) 400ml, and stirring to fully dissolve; loading to an erucic acid chromatographic column (100mm multiplied by 250mm, containing about 0.98kg of filler mass) balanced by eluent (water: ethanol is 10:90), loading at the flow rate of 200ml/min, eluting with eluent (water: ethanol is 10:90) at the flow rate of 400ml/min for 60min, collecting erucic acid component solution by HPLC detection, merging qualified components, concentrating to obtain 35.10g of pure erucic acid product with the detection purity of 95.88% and the recovery rate of 87.75%.
Comparative example 1
Taking 98g of crude erucic acid (the loading is 10 percent, m/m), the content is 65.87 percent (m/m), and adding water: ethanol (10: 90 (V/V)) 400ml, and stirring to fully dissolve; loading to an erucic acid chromatographic column (100mm multiplied by 250mm, containing about 0.98kg of filler mass) balanced by eluent (water: ethanol ═ 10:90), loading at the flow rate of 200ml/min, eluting with eluent (water: ethanol ═ 10:90) at the flow rate of 400ml/min, eluting for 60min, collecting erucic acid component solution by HPLC detection, merging qualified components, concentrating to obtain 11.10g of pure erucic acid product with the detection purity of 96.32% and the recovery rate of 11.33%.
Comparative example 2
Taking 40g of crude erucic acid with the content of 65.87% (m/m), adding water: ethanol (10: 90 (V/V)) 400ml, and stirring to fully dissolve; loading the obtained product on a Sepax-BR-C18 chromatographic column (100mm multiplied by 250mm, and the product number of the filler is 102180-3012) after the balance of eluent (water: ethanol ═ 10:90), eluting at the flow rate of 200ml/min by using eluent (water: ethanol ═ 10:90) after the sample loading, wherein the flow rate of the eluent is 400ml/min, eluting for 60min, collecting erucic acid component solution by HPLC detection, merging qualified components, concentrating to obtain 25.10g of pure erucic acid, wherein the detection purity is 95.73%, and the recovery rate is 62.75%.
Comparative example 3
Taking 40g of crude erucic acid with the content of 65.87% (m/m), adding water: ethanol (10: 90 (V/V)) 400ml, and stirring to fully dissolve; loading the obtained product on a Sepax-PolyRP chromatographic column (100mm multiplied by 250mm, filler cargo number: 263300-0000) after eluent (water: ethanol ═ 10:90) balance, eluting at the flow rate of 200ml/min, then eluting with eluent (water: ethanol ═ 10:90) at the flow rate of 400ml/min for 60min, collecting erucic acid component solution by HPLC detection, merging qualified components, concentrating to obtain 21.25g of pure erucic acid, wherein the detection purity is 96.17%, and the recovery rate is 53.13%.
As can be seen from examples 1 to 3 and comparative examples 1 to 3: the method for purifying the erucic acid provided by the invention is simple to operate, the used reagent is low in environmental pollution and energy consumption, and the process is feasible through pilot test verification. The loading capacity of the erucic acid is preferably not more than 10 percent, the purity of the obtained pure erucic acid is high, the total purity is higher than 95 percent, and the yield is higher than 86 percent.
From the above examples, the present invention provides an erucic acid purification method suitable for industrial scale-up production, comprising the following steps: dissolving the erucic acid crude product in a solvent to obtain an erucic acid crude product sample solution; loading the erucic acid crude product loading liquid into an erucic acid preparation column; the filler in the erucic acid preparation column takes silica gel as a matrix, and octadecylsilane and divinylbenzene are bonded on the silica gel; eluting the erucic acid preparation column with the eluent, collecting the elution components, merging the qualified eluents, and concentrating to obtain the purified erucic acid. The invention adopts the purification method to purify the erucic acid, has simple operation and is suitable for large-scale production. The experimental results show that: the purity of the purified erucic acid is higher than 95 percent, and the yield is higher than 86 percent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. An erucic acid purification method suitable for industrial amplification production comprises the following steps:
dissolving the erucic acid crude product in a solvent to obtain an erucic acid crude product sample solution;
loading the erucic acid crude product loading liquid into an erucic acid preparation column; the filler in the erucic acid preparation column takes silica gel as a matrix, and octadecylsilane and divinylbenzene are bonded on the silica gel;
eluting the erucic acid preparation column with the eluent, collecting the elution components, merging the qualified eluents, and concentrating to obtain the purified erucic acid.
2. The method for purifying erucic acid according to claim 1, wherein the solvent is a mixed solution of an organic solvent and water in a volume ratio of 0-20: 80-100;
the organic solvent is selected from one or more of methanol, ethanol and acetonitrile.
3. The method for purifying erucic acid according to claim 1, wherein the mass ratio of octadecylsilane to divinylbenzene is 1-10: 1.
4. The erucic acid purification method according to claim 1, wherein the eluent is a mixed solution of an organic solvent and water in a volume ratio of 0-20: 80-100;
the organic solvent is selected from one or more of methanol, ethanol and acetonitrile.
5. The method for purifying erucic acid according to claim 1, wherein the purity of the erucic acid in the qualified eluent is higher than 95%.
6. The method for purifying erucic acid according to claim 1, wherein the content of erucic acid in the crude erucic acid is 35-75%; the concentration of the erucic acid crude product loading liquid is 50-100 mg/ml; the loading does not exceed 10%.
7. The method for purifying erucic acid according to claim 1, wherein the flow rate of the sample loading is 10-400 ml/min; the flow rate of elution is 10-400 ml/min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009063500A2 (en) * | 2007-09-19 | 2009-05-22 | V.B.Medicare Pvt. Ltd. | Novel methods of isolation of poly unsaturated fatty acids |
| CN102921192A (en) * | 2012-05-16 | 2013-02-13 | 中国计量科学研究院 | Method for preparing high purity monounsaturated fatty acid |
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| JPS6137752A (en) * | 1984-07-30 | 1986-02-22 | Kuraray Co Ltd | Separation and purification of highly unsaturated long-chain fatty acid or its ester |
| JPS61291540A (en) * | 1985-06-19 | 1986-12-22 | Tama Seikagaku Kk | Separation and purification of long-chain highly unsaturated fatty acid or lower alkyl ester thereof |
| CN105272844B (en) * | 2014-06-09 | 2017-05-17 | 河北海德生物科技有限公司 | Method for purifying high-purity fish oil EPA(eicosapentaenoic acid) ethyl ester and DHA(docosahexaenoic acid) ethyl ester |
| CN108409555B (en) * | 2018-01-16 | 2021-08-10 | 杭州泽达健康科技有限公司 | Method for separating and refining nervonic acid |
| CN108624402B (en) * | 2018-04-17 | 2020-09-25 | 浙江大学 | Supercritical extraction method of erucic acid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009063500A2 (en) * | 2007-09-19 | 2009-05-22 | V.B.Medicare Pvt. Ltd. | Novel methods of isolation of poly unsaturated fatty acids |
| CN102921192A (en) * | 2012-05-16 | 2013-02-13 | 中国计量科学研究院 | Method for preparing high purity monounsaturated fatty acid |
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