CN111410606A - Process for preparing 2-hydroxycaproic acid and/or its polymer - Google Patents
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- CN111410606A CN111410606A CN202010106813.4A CN202010106813A CN111410606A CN 111410606 A CN111410606 A CN 111410606A CN 202010106813 A CN202010106813 A CN 202010106813A CN 111410606 A CN111410606 A CN 111410606A
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Abstract
The invention relates to a preparation method of 2-hydroxycaproic acid and/or a polymer thereof, belonging to the technical field of chemical analysis. The invention aims to solve the problems of high production cost and complex preparation process caused by the fact that 2-hydroxycaproic acid and/or polymers thereof can only be prepared by a microbial fermentation method or a chemical synthesis method in the prior art, and the technical scheme is to provide a preparation method of 2-hydroxycaproic acid and/or polymers thereof, namely the preparation method is obtained by separating from yellow water. The application of the invention provides a low-cost and convenient way for obtaining the 2-hydroxycaproic acid and/or the polymer thereof, can realize the resource recovery of the brewing by-product yellow water, is beneficial to reducing the discharge of the brewing production waste liquid, and has remarkable social benefit and environmental protection benefit.
Description
Technical Field
The invention relates to a preparation method of 2-hydroxycaproic acid and/or a polymer thereof, belonging to the technical field of chemical analysis.
Background
2-hydroxycaproic acid, CAS NO: 6064-63-7, molecular weight: 132.1577, is a hydroxy fatty acid compound, and its chemical structure is as follows:
hydroxy fatty acids contain both hydroxyl and carboxyl groups in their structure, which are susceptible to intramolecular and intermolecular polymerization, thereby forming Polyhydroxyalkanoates (PHAs). The polyhydroxyalkanoate not only shows the properties of chemical synthetic plastics, but also has special performances such as good biodegradability and biocompatibility, and has wide application prospect. At present, the research of the PHAs microbial synthesis route always occupies the leading position in the field, but the PHAs cannot compete with petrochemical synthetic plastics due to the restriction of factors such as high fermentation cost and the like, so that the application market is difficult to widen.
Yellow water is a brownish yellow and slightly viscous turbid liquid generated by opening and opening a cellar and dropping the cellar in the brewing process of the strong aromatic Chinese spirits, belongs to a brewing byproduct and is usually discharged as waste liquid. Yellow water is rich in nutrients required by microorganisms such as saccharides, acids, proteins and the like and aroma components of strong-flavor liquor, and at present, the acids are mainly lactic acid, and related researches on recycling of the yellow water lactic acid are known. However, no research report on the separation preparation of 2-hydroxycaproic acid from yellow water has been found so far.
Disclosure of Invention
The invention aims to provide a preparation method of 2-hydroxycaproic acid and/or a polymer thereof, which aims to solve the problems of high production cost and complex preparation process caused by the fact that the 2-hydroxycaproic acid and/or the polymer thereof can only be prepared by a microbial fermentation method or a chemical synthesis method in the prior art.
The invention provides a preparation method of 2-hydroxycaproic acid and/or a polymer thereof, which comprises the following steps: is separated from yellow water.
Further, the preparation method comprises the following steps: a. extracting yellow water with organic solvent, and concentrating to obtain crude extract; b. subjecting the crude extract to normal phase chromatography, collecting eluate containing 2-hydroxycaproic acid and/or its polymer, and concentrating to obtain crude product; c. separating the crude product by reverse phase chromatography, collecting eluate containing 2-hydroxycaproic acid and/or its polymer, and concentrating.
In the preparation method, firstly, the yellow water is extracted by an organic solvent, so that the 2-hydroxycaproic acid and the polymer thereof can be extracted, and simultaneously, impurities such as starch, sugar, protein and the like are prevented from entering an extracting solution; then carrying out normal phase chromatography, wherein the principle is that the separation is carried out according to the different polarities of the compounds, thereby achieving the purpose of separating and purifying the 2-hydroxycaproic acid and the polymer thereof; and finally, performing reversed-phase chromatographic separation, wherein the principle is that further purification is performed according to different polarities of the compounds, so that the aim of improving the purity of the 2-hydroxycaproic acid and the polymer thereof is fulfilled. By combining the above separation means, it is possible to separate high purity 2-hydroxycaproic acid and its polymer from yellow water having a complex composition.
Further, the organic solvent in step a is ethyl acetate. The ethyl acetate is used for simple extraction, so that the extraction rate of the 2-hydroxycaproic acid in the yellow water can reach more than 90 percent, and macromolecular components such as starch, protein and the like are prevented from entering the extracting solution as far as possible.
Further, when the organic solvent in step a is ethyl acetate, the extraction in step a satisfies at least one of the following conditions:
the extraction times are 2-3 times;
for each extraction, ethyl acetate: the volume ratio of the yellow water is (2:1) - (4: 1);
the extraction temperature is 10-30 ℃;
for each extraction, the extraction time is 3-5 min;
the extraction method is selected from shaking extraction or ultrasonic extraction.
Wherein, for each extraction, ethyl acetate: the volume ratio of the yellow water is preferably (2:1) to (4:1), so that the 2-hydroxycaproic acid and the polymer thereof in the yellow water can be sufficiently extracted, and the waste of the solvent is not caused.
The extraction temperature is preferably 10-30 ℃, so that the 2-hydroxycaproic acid and polymers thereof in the yellow water can be fully extracted, macromolecular components such as starch, protein and the like can be prevented from entering an extracting solution as far as possible, and the solvent cannot be seriously volatilized and excessively lost.
Wherein the extraction times are preferably 2-3 times; for each extraction, the extraction time is preferably 3-5 min; the extraction mode is preferably shaking extraction or ultrasonic extraction. Therefore, the 2-hydroxycaproic acid and the polymer thereof in the yellow water can be fully extracted, and the waste of organic solvent and the prolonging of extraction time can not be caused.
Further, step a is concentrated at 40-80 ℃.
Further, the normal phase chromatography of step b satisfies at least one of the following:
the stationary phase adopts normal phase silica gel;
preferably, the normal phase silica gel is 100 meshes;
further preferably, the normal phase silica gel is 300 meshes;
taking ethyl acetate and n-butanol as elution reagents;
preferably, the gradient elution is performed in the following ratios in sequence: 80:1, 50:1, 20:1, 10:1, ethyl acetate: n-butanol, v/v;
further preferably, the elution amount per ratio: the yellow water taken in the step a is (4-5): 20, v/v.
Wherein, the normal phase silica gel is preferably 100 meshes. Further preferably, the normal phase silica gel is 300 meshes. Therefore, a better purification effect can be achieved, and the separation speed can be ensured.
Wherein, ethyl acetate and n-butanol are used as elution reagents, and different compounds in the crude extract can be gradually eluted from weak polarity to strong polarity through gradient elution.
Further, the reverse phase chromatographic separation of step c satisfies at least one of the following:
adopting preparative chromatography;
the stationary phase is a C18 column;
methanol and/or ethanol and water are used as elution reagents;
preferably, the gradient elution is performed as follows: 0-5 min: 10% v/v methanol; 5.1-20 min: 10-100% v/v methanol; 20.1-25 min: 100% v/v methanol; 25.1-27 min: 10% v/v methanol, stop elution; or: 0-6 min: 10% v/v methanol; 6.1-20 min: 10-100% v/v methanol; 20.1-25 min: 100% v/v methanol; 25.1-27 min: 10% v/v methanol, stop elution;
the chromatographic flow rate is 10-20 m L/min, and the sample injection amount is 1-10 m L;
preferably, the chromatographic flow rate is 10m L/min and the sample size is 5m L.
Further, the polymer is a polymer of 2-6 molecules of 2-hydroxycaproic acid.
Further, the yellow water is produced by brewing the Luzhou-flavor liquor.
Wherein, the reversed phase chromatographic separation in the step C preferably adopts a C18 column as a stationary phase; preferably, methanol and/or ethanol and water are used as elution reagents; preferably, a gradient elution is used. Therefore, the separation can be carried out according to the polarity of the compounds in the sample, the column with large polarity is weak in retention and is eluted firstly, and the column with small polarity is strong in retention and is eluted later. Meanwhile, the scheme has high separation efficiency and high product purity.
The invention provides a method for separating and preparing 2-hydroxycaproic acid and/or a polymer thereof from yellow water, which mainly has the following advantages:
1. the economic benefit is obvious. The yellow water belongs to a byproduct generated in the process of brewing the white spirit, is usually treated as waste liquid and cannot be effectively utilized, and the preparation method provided by the invention realizes resource recovery of brewing wastes. In addition, the acquisition way of the 2-hydroxycaproic acid is usually microbial fermentation or chemical synthesis, the cost is high, the method is separated and prepared from yellow water, and the production cost is obviously reduced.
2. The preparation and separation method is simple and convenient, and the product purity is high. The preferred technical scheme of the invention combines various separation technologies such as organic solvent extraction, normal phase chromatography, reverse phase chromatography separation and the like, realizes the purification of the 2-hydroxycaproic acid and the polymer thereof, has mature technical route, and does not show obvious impurity peaks in a product chromatogram.
Drawings
FIG. 1 is a total ion flow diagram of liquid mass spectrometry of 2-hydroxyhexanoic acid and its polymer obtained in example 1;
FIG. 2 is a second-order mass spectrum of a target ion of the 2-hydroxycaproic acid monomer obtained in example 1;
FIG. 3 is a target ion secondary mass spectrum of two 2-hydroxycaproic acid polymers obtained in example 1;
FIG. 4 is a target ion secondary mass spectrum of three 2-hydroxycaproic acid polymers obtained in example 1;
FIG. 5 is a target ion secondary mass spectrum of four 2-hydroxycaproic acid polymers obtained in example 1;
FIG. 6 is a target ion secondary mass spectrum of five 2-hydroxycaproic acid polymers obtained in example 1;
FIG. 7 is a target ion secondary mass spectrum of six 2-hydroxycaproic acid polymers obtained in example 1.
Detailed Description
The invention provides a preparation method of 2-hydroxycaproic acid and/or a polymer thereof, which comprises the following steps: is separated from yellow water.
The present invention has been completed based on the following findings of the inventors: in the process of exploring valuable components of brewing by-products, the inventor finds that hydroxycarboxylic acid existing in yellow water is mainly 2-hydroxycaproic acid and is not low in content, provides possibility for separating and preparing 2-hydroxycaproic acid and polymers thereof from the yellow water, and also provides a novel method for obtaining the compound in large quantity.
Furthermore, the invention creatively combines a plurality of separation technologies such as organic solvent extraction, normal phase chromatography, reverse phase chromatography separation and the like, and 2-hydroxycaproic acid and polymers thereof with the purity of more than 95 percent are separated from yellow water with complex components for the first time. The high-resolution high performance liquid chromatography-quadrupole time-of-flight mass spectrometry is adopted as a detection means to carry out qualitative analysis on a pure target compound, and the compound is determined to be 2-hydroxycaproic acid and a polymer thereof.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
EXAMPLE 1 isolation of 2-Hydroxyhexanoic acid from yellow Water and its polymers
(1) Taking yellow water 20L, adding 60L ethyl acetate each time, performing ultrasonic extraction at 20 deg.C for 3min, extracting for 3 times, and concentrating the extractive solution at 40 deg.C under reduced pressure to obtain ethyl acetate crude extract 200 g.
(2) And (3) uniformly stirring the ethyl acetate crude extract and 100-mesh normal phase silica gel, and performing normal phase column chromatography. Taking ethyl acetate and n-butanol as elution reagents, carrying out gradient elution according to the proportion of 80:1, 50:1, 20:1 and 10:1 (ethyl acetate: n-butanol and v/v) in sequence, eluting 4 liters in each proportion, and collecting the eluate once in each 1 liter. And (3) carrying out liquid phase mass spectrum detection on the eluent, combining the eluents determined to contain the 2-hydroxycaproic acid and the polymer thereof, concentrating under reduced pressure, and drying to obtain a crude product Y-12.
(3) Diluting the crude product Y-12 obtained in the step (2) with methanol, injecting a sample to prepare a chromatogram, wherein the sample injection amount is 5m L, a C18 column is used as a stationary phase, gradient elution is performed by using methanol and water as mobile phases, the gradient elution is performed by using 0-5 min: 10% v/v methanol, 5.1-20 min: 10-100% v/v methanol, 20.1-25 min: 100% v/v methanol, the gradient elution is stopped by using 25.1-27 min: 10% v/v methanol, the chromatographic flow rate is 10m L/min, a section with an absorption peak at 210nm is collected, the eluent is subjected to liquid mass spectrometry, the eluents determined to be 2-hydroxycaproic acid and polymers thereof are combined, and the mixture is concentrated under reduced pressure and dried to obtain a component Z-15.
(4) Dissolving the component Z-15 obtained in the step (3) in methanol, and determining the component Z-15 as a target compound through qualitative analysis of mass spectrum (L C-QTOF). The total ion flow diagram of liquid phase mass spectrum is shown in figure 1, [ M-H ]]+The compound of 131.0718 is 2-hydroxyhexanoic acid monomer with fragment ion 85.0670 (see FIG. 2); [ M-H ]]+The compound 245.1409 is a 2-hydroxyhexanoic acid dimer with a fragment ion of 131.0716, i.e., [ M-H ] of 2-hydroxyhexanoic acid monomer]+(see FIG. 3); [ M-H ]]+The compound 359.2102 is a polymer of three 2-hydroxycaproic acids with fragment ions 131.0716, i.e. [ M-H ] of the 2-hydroxycaproic acid monomer]+(see FIG. 4); [ M-H ]]+The compound 473.2784 is a polymer of four 2-hydroxycaproic acids with fragment ions 131.0715, 245.1404, i.e. [ M-H ] of the 2-hydroxycaproic acid monomer]+And dimeric [ M-H]+(see FIG. 5); [ M-H ]]+The compound 587.3463 is a polymer of five 2-hydroxycaproic acids with fragment ions 131.0718, 245.1399, 473.2773, i.e. [ M-H ] of the 2-hydroxycaproic acid monomer]+Dimeric [ M-H ]]+And tetrameric [ M-H]+(see FIG. 6); [ M-H ]]+The compound 701.4146 is a polymer of six 2-hydroxycaproic acids with fragment ions 131.0714, 245.1399, 473.2776, 587.3444, i.e. [ M-H ] of the monomers 2-hydroxycaproic acid]+Dimeric [ M-H ]]+Tetrameric [ M-H ]]+And five[ M-H ] of a Polymer]+(see FIG. 7).
The sample fraction Z-15 was dissolved in aqueous methanol to hydrolyze the polymer to the monomeric form, and the purity of 2-hydroxycaproic acid was 97% by mass spectrometry using a 2-hydroxycaproic acid standard as a reference.
EXAMPLE 2 isolation of 2-Hydroxyhexanoic acid from yellow Water and its polymers
(1) And (3) taking yellow water 20L, adding 80L ethyl acetate each time, carrying out ultrasonic extraction at 20 ℃ for 5min for 2 times, and concentrating the extract at 60 ℃ under reduced pressure to obtain 240g of ethyl acetate crude extract.
(2) And (3) uniformly stirring the ethyl acetate crude extract and 100-mesh normal phase silica gel, and performing normal phase column chromatography. Taking ethyl acetate and n-butanol as elution reagents, carrying out gradient elution according to the proportion of 80:1, 50:1, 20:1 and 10:1 (ethyl acetate: n-butanol and v/v) in sequence, wherein each proportion elutes 5 liters, and each 1 liter is separately collected. And (3) carrying out liquid phase mass spectrum detection on the eluent, combining the eluents determined to contain the 2-hydroxycaproic acid and the polymer thereof, concentrating under reduced pressure, and drying to obtain a crude product Y2-14.
(3) Diluting the crude product Y2-14 obtained in the step (2) with ethanol, injecting a sample to prepare a chromatogram, wherein the sample injection amount is 5m L, a C18 column is used as a stationary phase, gradient elution is carried out by using ethanol and water as mobile phases, the gradient elution is carried out for 0-6 min: 10% v/v methanol, 6.1-20 min: 10-100% v/v methanol, 20.1-25 min: 100% v/v methanol, 25.1-27 min: 10% v/v methanol, the elution is stopped, the chromatographic flow rate is 10m L/min, a section with an absorption peak at 210nm is collected, the eluent is subjected to liquid mass spectrometry, the eluents determined to be 2-hydroxycaproic acid and polymers thereof are combined, decompressed, concentrated and dried, and the component Z2-21 is obtained.
(4) Dissolving the component Z2-21 obtained in the step (3) in methanol, and determining the component as a target compound through mass spectrum (L C-QTOF) qualitative analysis]+The compound of 131.0718 is 2-hydroxyhexanoic acid monomer with fragment ion 85.0670; [ M-H ]]+The compound 245.1409 is a 2-hydroxyhexanoic acid dimer with a fragment ion of 131.0716, i.e., [ M-H ] of 2-hydroxyhexanoic acid monomer]+；[M-H]+The compound 359.2102 is a polymer of three 2-hydroxyhexanoic acids, the fragments of which are isolatedSeed is 131.0716, [ M-H ] of 2-hydroxycaproic acid monomer]+；[M-H]+The compound 473.2784 is a polymer of four 2-hydroxycaproic acids with fragment ions 131.0715, 245.1404, i.e. [ M-H ] of the 2-hydroxycaproic acid monomer]+And dimeric [ M-H]+；[M-H]+The compound 587.3463 is a polymer of five 2-hydroxycaproic acids with fragment ions 131.0718, 245.1399, 473.2773, i.e. [ M-H ] of the 2-hydroxycaproic acid monomer]+Dimeric [ M-H ]]+And tetrameric [ M-H]+；[M-H]+The compound 701.4146 is a polymer of six 2-hydroxycaproic acids with fragment ions 131.0714, 245.1399, 473.2776, 587.3444, i.e. [ M-H ] of the monomers 2-hydroxycaproic acid]+Dimeric [ M-H ]]+Tetrameric [ M-H ]]+And pentameric [ M-H]+。
The sample fraction Z-21 was dissolved in aqueous methanol to hydrolyze the polymer to the monomeric form, and the purity of 2-hydroxycaproic acid was 97% by mass spectrometry using a 2-hydroxycaproic acid standard as a reference.
It should be appreciated that the particular features, structures, materials, or characteristics described in this specification may be combined in any suitable manner in any one or more embodiments. Furthermore, the various embodiments and features of the various embodiments described in this specification can be combined and combined by one skilled in the art without contradiction.
Claims (9)
- A process for preparing 2-hydroxycaproic acid and/or polymers thereof, characterized in that: is separated from yellow water.
- 2. The method of claim 1, wherein: the method comprises the following steps: a. extracting yellow water with organic solvent, and concentrating to obtain crude extract; b. subjecting the crude extract to normal phase chromatography, collecting eluate containing 2-hydroxycaproic acid and/or its polymer, and concentrating to obtain crude product; c. separating the crude product by reverse phase chromatography, collecting eluate containing 2-hydroxycaproic acid and/or its polymer, and concentrating.
- 3. The method of claim 2, wherein: the organic solvent in the step a is ethyl acetate.
- 4. The method of claim 3, wherein: the extraction in the step a meets at least one of the following conditions:the extraction times are 2-3 times;for each extraction, ethyl acetate: the volume ratio of the yellow water is (2:1) - (4: 1);the extraction temperature is 10-30 ℃;for each extraction, the extraction time is 3-5 min;the extraction method is selected from shaking extraction or ultrasonic extraction.
- 5. The method of claim 2, wherein: step a, concentrating at 40-80 ℃.
- 6. The method of claim 2, wherein: the normal phase chromatography in the step b meets at least one of the following conditions:the stationary phase adopts normal phase silica gel;preferably, the normal phase silica gel is 100 meshes;further preferably, the normal phase silica gel is 300 meshes;taking ethyl acetate and n-butanol as elution reagents;preferably, the gradient elution is performed in the following ratios in sequence: 80:1, 50:1, 20:1, 10:1, ethyl acetate: n-butanol, v/v;further preferably, the elution amount per ratio: the yellow water taken in the step a is (4-5): 20, v/v.
- 7. The method of claim 2, wherein: the reversed phase chromatographic separation of the step c meets at least one of the following conditions:adopting preparative chromatography;the stationary phase is a C18 column;methanol and/or ethanol and water are used as elution reagents;preferably, the gradient elution is performed as follows: 0-5 min: 10% v/v methanol; 5.1-20 min: 10-100% v/v methanol; 20.1-25 min: 100% v/v methanol; 25.1-27 min: 10% v/v methanol, stop elution; or: 0-6 min: 10% v/v methanol; 6.1-20 min: 10-100% v/v methanol; 20.1-25 min: 100% v/v methanol; 25.1-27 min: 10% v/v methanol, stop elution;the chromatographic flow rate is 10-20 m L/min, and the sample injection amount is 1-10 m L;preferably, the chromatographic flow rate is 10m L/min and the sample size is 5m L.
- 8. The method according to any one of claims 1 to 7, wherein: the polymer is a polymer of 2-6 molecules of 2-hydroxycaproic acid.
- 9. The method according to any one of claims 1 to 7, wherein: the yellow water is produced by brewing the strong aromatic Chinese spirits.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321516A (en) * | 2011-08-31 | 2012-01-18 | 重庆诗仙太白酒业（集团）有限公司 | Processing technology for secondary utilization of organic matter in solid-state fermentation of Luzhou-flavour liquor |
| CN102533482A (en) * | 2012-02-16 | 2012-07-04 | 泸州品创科技有限公司 | Method for recycling yellow water |
| CN102924263A (en) * | 2012-11-08 | 2013-02-13 | 中国天辰工程有限公司 | Method for preparing 6-hydroxy caproic acid |
| CN102987063A (en) * | 2012-11-28 | 2013-03-27 | 张有聪 | Organic acid animal growth regulator and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321516A (en) * | 2011-08-31 | 2012-01-18 | 重庆诗仙太白酒业（集团）有限公司 | Processing technology for secondary utilization of organic matter in solid-state fermentation of Luzhou-flavour liquor |
| CN102533482A (en) * | 2012-02-16 | 2012-07-04 | 泸州品创科技有限公司 | Method for recycling yellow water |
| CN102924263A (en) * | 2012-11-08 | 2013-02-13 | 中国天辰工程有限公司 | Method for preparing 6-hydroxy caproic acid |
| CN102987063A (en) * | 2012-11-28 | 2013-03-27 | 张有聪 | Organic acid animal growth regulator and preparation method thereof |
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