CN112125798B - Erucic acid purifying method suitable for industrial scale-up production - Google Patents
Erucic acid purifying method suitable for industrial scale-up production Download PDFInfo
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- CN112125798B CN112125798B CN202011025604.3A CN202011025604A CN112125798B CN 112125798 B CN112125798 B CN 112125798B CN 202011025604 A CN202011025604 A CN 202011025604A CN 112125798 B CN112125798 B CN 112125798B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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 a erucic acid purifying method suitable for industrial large-scale production, which comprises the following steps: dissolving the erucic acid crude product in a solvent to obtain erucic acid crude product sample liquid; loading the erucic acid crude product loading liquid into an erucic acid preparation column; the packing in the erucic acid preparation column takes silica gel as a matrix, and octadecylsilane and divinylbenzene are bonded on the silica gel; eluting the sample-loaded erucic acid preparation column by using eluent, collecting elution components, combining qualified eluents, and concentrating to obtain purified erucic acid. The method for purifying the erucic acid is simple to operate and suitable for large-scale production. The invention provides a low-energy erucic acid purifying method from the perspective of chromatographic purification, and provides a basis for feasibility through pilot test verification. The experimental results show that: the purity of the erucic acid after purification is higher than 95%, and the yield is higher than 86%.
Description
Technical Field
The invention belongs to the technical field of purification, and particularly relates to a erucic acid purification method suitable for industrial large-scale production.
Background
Erucic acid, cis-13-docosenoic acid, of formula: c (C) 22 H 42 O 2 . Erucic acid is a soft solid monounsaturated fatty acid, is white needle-shaped crystal at normal temperature, is very easy to dissolve in diethyl ether, is dissolved in ethanol and methanol, and is insoluble in water. Erucic acid is mainly used for producing erucamide, and can also be used for preparing various surfactants, cosmetics, chemical fiber oiling agents and the like. Erucic acid is present in large amounts in the form of glyceric acid in oils such as rape oil, sea blue oil, mustard oil and the like. The erucic acid molecular carbon chain is longer than oleic acid and linolenic acid, and has stronger hydrophobicity, waterproofness and excellent lubricity. Erucic acid itself oxidizes and polymerizes at a much slower rate than the carbon chain. Derivatives thereof find application in many fields, such as antistatic agents, lubricants, plasticizers, light and heat stabilizers, antiblocking agents, synthetic resins (nylon 1313), synthetic fragrances, and the like. Erucic acid plays a great role in a plurality of modern industrial fields by virtue of the advantages of wide application, high added value, great market demand, renewable property and the like, and is honored as an important fine chemical raw material in the 21 st century.
Most of erucic acid purification adopts a rectification method, so that the process is complex and the energy consumption is high.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for purifying erucic acid suitable for industrial scale-up production, which is simple and can be used for scale-up production.
The invention provides a erucic acid purifying method suitable for industrial large-scale production, which comprises the following steps:
dissolving the erucic acid crude product in a solvent to obtain erucic acid crude product sample liquid;
loading the erucic acid crude product loading liquid into an erucic acid preparation column; the packing in the erucic acid preparation column takes silica gel as a matrix, and octadecylsilane and divinylbenzene are bonded on the silica gel;
eluting the sample-loaded erucic acid preparation column by using eluent, collecting elution components, combining qualified eluents, and concentrating to obtain 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 eluent is higher than 95%.
Preferably, the erucic acid content in the erucic acid crude product is 35-75%; the concentration of the erucic acid crude product sample liquid is 50-100 mg/ml; the loading of the sample is not more than 10%.
Preferably, the flow rate of the sample loading is 10-400 ml/min; the flow rate of the elution is 10-400 ml/min.
The invention provides a erucic acid purifying method suitable for industrial large-scale production, which comprises the following steps: dissolving the erucic acid crude product in a solvent to obtain erucic acid crude product sample liquid; loading the erucic acid crude product loading liquid into an erucic acid preparation column; the packing in the erucic acid preparation column takes silica gel as a matrix, and octadecylsilane and divinylbenzene are bonded on the silica gel; eluting the sample-loaded erucic acid preparation column by using eluent, collecting elution components, combining qualified eluents, and concentrating to obtain purified erucic acid. The method for purifying the erucic acid is simple to operate and suitable for large-scale production. The invention provides a low-energy erucic acid purifying method from the perspective of chromatographic purification, and provides a basis for feasibility through pilot test verification. The experimental results show that: the purity of the erucic acid after purification is higher than 95%, and the yield is higher than 86%.
Drawings
FIG. 1A liquid chromatogram of the crude erucic acid purification process provided in example 1 of the invention.
Detailed Description
The invention provides a erucic acid purifying method suitable for industrial large-scale production, which comprises the following steps:
dissolving the erucic acid crude product in a solvent to obtain erucic acid crude product sample liquid;
loading the erucic acid crude product loading liquid into an erucic acid preparation column; the packing in the erucic acid preparation column takes silica gel as a matrix, and octadecylsilane and divinylbenzene are bonded on the silica gel;
eluting the sample-loaded erucic acid preparation column by using eluent, collecting elution components, combining qualified eluents, and concentrating to obtain purified erucic acid.
In the invention, the mass content of erucic acid in the erucic acid crude product is 35-75%; in a specific example, the erucic acid crude product has a erucic acid content of 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 mixed solution of water and acetonitrile in a volume ratio of 12:88; or a 10:90 volume ratio of water to methanol. The concentration of the erucic acid crude product sample liquid is 50-100 mg/ml; in a specific embodiment, the concentration of the erucic acid crude product loading liquid is 100mg/ml.
The method comprises the steps of loading the erucic acid crude product loading liquid into an erucic acid preparation column; the packing 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 octadecylsilane and divinylbenzene account for 15% -19% of the mass of the silica gel. The loading of the sample is not more than 10%, preferably 4-8%. The flow rate of the sample is 10-400 ml/min; in specific embodiments, the loading flow rate is 200ml/min, or 400ml/min.
The invention adopts eluent to elute the sample-loaded erucic acid preparation column, collects elution components, combines qualified eluents, and concentrates to obtain purified erucic acid. 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 mixed solution of water and acetonitrile in a volume ratio of 12:88; or a mixed solution of water and methanol in a volume ratio of 10:90. The flow rate of the elution is 10-400 ml/min; in a specific embodiment, the elution flow rate is 400ml/min.
In the invention, the erucic acid content in the qualified eluent is higher than 95%.
In order to further illustrate the present invention, a method for purifying erucic acid suitable for industrial scale-up production is described in detail below with reference to examples, but they should not be construed as limiting the scope of the invention.
1. Instrument and materials
Crude erucic acid, sepax prepared liquid chromatograph LC6000, analytical balance (one hundredth), analytical balance (one ten thousandth), volumetric flask (10 ml), pipette 1ml and 200 μl each (gun head), magnetic stirrer, vortex mixer, measuring cylinder (500 ml, 100 ml), disposable dropper and 5ml centrifuge tube each pack, 2L conical flask, preservative film, marker pen, label paper, etc.;
2. reagent(s)
Methanol (analytically pure), acetonitrile (analytically pure), ethanol (analytically pure), 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 configuration: preparing a proper amount of organic solvent-water mixed solution;
(3) Sample dissolution: adding a proper amount of the solvent prepared in the step (2) into the erucic acid crude product in the step (1), sealing by using a preservative film, adding a stirrer, keeping a stirring state on a magnetic stirrer, fully mixing, and then fixing the volume for later use;
(4) Column equilibrium: on an LC6000 instrument, under the condition of connecting the erucic acid preparation column, washing the balance column with eluent, and balancing;
(5) Sample loading: stopping all pumps after the step (4) is finished, inserting a pipeline into the solvent prepared in the step (2), flushing the pipeline, stopping the pump, replacing the pipeline into the prepared erucic acid crude product, stopping the pump after the sample is completely loaded, replacing the pipeline into the solvent left in the step (2), and stopping the pump after flushing;
(6) Sample elution: after the step 5 is completed, the pump pipeline is replaced into eluent, and meanwhile, the online signal record of the preparation workstation is started to start elution;
(7) Sample collection: samples were collected starting at the point where the peak of interest was seen to occur, every 2 min. See sample preparation figures in detail;
(8) And collecting analysis detection of the samples and combining qualified samples.
Example 1
Chromatographic column erucic acid preparation column (100 mm. Times.250 mm);
eluent, namely water: methanol=8: 92;
the flow rate is 400ml/min, the sample injection amount is 400ml, and the column temperature is room temperature;
sample 100mg/ml pressure 1.1M Pa;
the instrument is Sepax preparative chromatograph LC6000;
the detection wavelength is UV@214 nm;
the specific method comprises the following steps:
1. weighing a sample: 40g of crude erucic acid is weighed on an analytical balance;
2. preparing a solvent: preparing 92% methanol water solution with proper amount for standby;
3. sample dissolution: adding a proper amount of the solvent prepared in the step 2 into 40g of crude erucic acid, sealing with a preservative film, adding a stirrer, keeping a stirring state on a magnetic stirrer, fully mixing, fixing the volume to 400ml, and uniformly mixing for later use;
4. column equilibrium: washing the equilibrated column with eluent at a flow rate of 400ml/min on an LC6000 instrument under conditions of switching on the erucic acid preparation column, equilibration for 15min;
5. sample loading: stopping all pumps after the step 4 is completed, replacing the pipeline into the prepared erucic acid crude product, loading the sample at the speed of 400ml/min for 1min, and stopping the pumps;
6. sample elution: after the step 5 is completed, the pump pipeline is replaced into eluent, meanwhile, the online signal record of the preparation workstation is started, and elution is started under the condition of 400ml/min;
7. sample collection: the sample collection was started when the appearance of the target peak was seen. As shown in fig. 1, collecting components with retention time of 14-32 min;
8. collecting sample analysis and detection and qualified sample combination;
9. the data during purification are shown in table 1:
table 1 example 1 statistical results of data before and after purification
。
Example 2
40g of crude erucic acid with the content of 65.87% (m/m) is taken and water is used for: acetonitrile=12:88 (V/V) 400ml, stirred to dissolve well; loading onto erucic acid chromatographic column (100 mm×250mm, containing filler with mass of about 0.98 kg) equilibrated with eluent (water: acetonitrile=12:88), loading at 200ml/min, eluting with eluent (water: acetonitrile=12:88), at 400ml/min, co-eluting for 60min, detecting by HPLC, collecting erucic acid component solution, mixing qualified components, concentrating to obtain erucic acid pure product 34.57g, detecting purity 95.71%, and recovery 86.43%.
Example 3
40g of crude erucic acid with the content of 65.87% (m/m) is taken and water is used for: ethanol=10:90 (V/V) 400ml, stirred to dissolve well; loading onto erucic acid chromatographic column (100 mm×250mm, containing filler with mass of about 0.98 kg) equilibrated with eluent (water: ethanol=10:90), eluting with eluent (water: ethanol=10:90) at 200ml/min, eluting at 400ml/min, co-eluting for 60min, detecting and collecting erucic acid component solution by HPLC, mixing qualified components, concentrating to obtain erucic acid pure product 35.10g, detecting purity 95.88%, and recovering rate 87.75%.
Comparative example 1
98g (load 10%, m/m) of crude erucic acid product with a content of 65.87% (m/m) is taken, and water is used: ethanol=10:90 (V/V) 400ml, stirred to dissolve well; loading onto erucic acid chromatographic column (100 mm×250mm, containing filler with mass of about 0.98 kg) equilibrated with eluent (water: ethanol=10:90), eluting with eluent (water: ethanol=10:90) at 200ml/min, eluting at 400ml/min, co-eluting for 60min, detecting and collecting erucic acid component solution by HPLC, mixing qualified components, concentrating to obtain erucic acid pure product 11.10g, detecting purity 96.32%, and recovering rate 11.33%.
Comparative example 2
40g of crude erucic acid with the content of 65.87% (m/m) is taken and water is used for: ethanol=10:90 (V/V) 400ml, stirred to dissolve well; loading onto Sepax-BR-C18 chromatographic column (100 mm×250mm, packing number: 102180-3012) equilibrated with eluent (water: ethanol=10:90), eluting with eluent (water: ethanol=10:90) at 200ml/min, eluting at 400ml/min, co-eluting for 60min, detecting and collecting erucic acid component solution by HPLC, mixing qualified components, concentrating to obtain erucic acid pure product 25.10g, detecting purity 95.73%, and recovering rate 62.75%.
Comparative example 3
40g of crude erucic acid with the content of 65.87% (m/m) is taken and water is used for: ethanol=10:90 (V/V) 400ml, stirred to dissolve well; loading on Sepax-PolyRP chromatographic column (100 mm×250mm, packing number: 263300-0000) equilibrated with eluent (water: ethanol=10:90), eluting with eluent (water: ethanol=10:90) at 200ml/min, eluting at 400ml/min, co-eluting for 60min, collecting erucic acid component solution by HPLC detection, mixing qualified components, concentrating to obtain 21.25g erucic acid pure product with detection purity of 96.17%, and recovery rate of 53.13%.
It can be seen from examples 1 to 3 and comparative examples 1 to 3 that: the method for purifying the erucic acid is simple to operate, the used reagent has small environmental pollution and low energy consumption, and the technology is feasible through pilot test verification. The loading capacity of the erucic acid is preferably not more than 10%, the purity of the obtained erucic acid pure product is high, the total purity is higher than 95%, and the yield is higher than 86%.
From the above examples, the present invention provides a method for purifying erucic acid suitable for industrial scale-up production, comprising the following steps: dissolving the erucic acid crude product in a solvent to obtain erucic acid crude product sample liquid; loading the erucic acid crude product loading liquid into an erucic acid preparation column; the packing in the erucic acid preparation column takes silica gel as a matrix, and octadecylsilane and divinylbenzene are bonded on the silica gel; eluting the sample-loaded erucic acid preparation column by using eluent, collecting elution components, combining qualified eluents, and concentrating to obtain purified erucic acid. The method for purifying the erucic acid is simple to operate and suitable for large-scale production. The experimental results show that: the purity of the erucic acid after purification is higher than 95%, and the yield is higher than 86%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (4)
1. A erucic acid purifying method suitable for industrial scale-up production comprises the following steps:
dissolving the erucic acid crude product in a solvent to obtain erucic acid crude product sample liquid;
loading the erucic acid crude product loading liquid into an erucic acid preparation column; the packing in the erucic acid preparation column takes silica gel as a matrix, and octadecylsilane and divinylbenzene are bonded on the silica gel;
eluting the sample-loaded erucic acid preparation column by adopting eluent, collecting elution components, combining qualified eluents, and concentrating to obtain purified erucic acid;
the solvent is a mixed solution of an organic solvent and water in a volume ratio of 0-20:80-100; and the volume of the organic solvent in the solvent is not 0;
the organic solvent in the solvent is selected from one or more of methanol, ethanol and acetonitrile;
the mass ratio of the octadecylsilane to the divinylbenzene is 1-10:1;
the eluent is a mixed solution of an organic solvent and water in a volume ratio of 0-20:80-100; and the volume of the organic solvent in the eluent is not 0;
the organic solvent in the eluent is selected from one or more of methanol, ethanol and acetonitrile.
2. The method of purifying erucic acid of claim 1, wherein the purity of erucic acid in the qualified eluate is greater than 95%.
3. The method for purifying erucic acid according to claim 1, wherein the erucic acid content in the crude erucic acid is 35-75%; the concentration of the erucic acid crude product sample liquid is 50-100 mg/ml; the loading of the sample is not more than 10%.
4. The method for purifying erucic acid according to claim 1, wherein the flow rate of the sample is 10-400 ml/min; the flow rate of the elution is 10-400 ml/min.
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Citations (7)
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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 |
| 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 |
| CN105272844A (en) * | 2014-06-09 | 2016-01-27 | 北京创新通恒科技有限公司 | Method for purifying high-purity fish oil EPA(eicosapentaenoic acid) ethyl ester and DHA(docosahexaenoic acid) ethyl ester |
| CN108409555A (en) * | 2018-01-16 | 2018-08-17 | 杭州泽达健康科技有限公司 | The method of separation and purification nervonic acid |
| CN108624402A (en) * | 2018-04-17 | 2018-10-09 | 浙江大学 | A kind of method of means of supercritical extraction erucic acid |
-
2020
- 2020-09-25 CN CN202011025604.3A patent/CN112125798B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN105272844A (en) * | 2014-06-09 | 2016-01-27 | 北京创新通恒科技有限公司 | Method for purifying high-purity fish oil EPA(eicosapentaenoic acid) ethyl ester and DHA(docosahexaenoic acid) ethyl ester |
| CN108409555A (en) * | 2018-01-16 | 2018-08-17 | 杭州泽达健康科技有限公司 | The method of separation and purification nervonic acid |
| CN108624402A (en) * | 2018-04-17 | 2018-10-09 | 浙江大学 | A kind of method of means of supercritical extraction erucic acid |
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