Method for separating and purifying organic alcohol and application thereof

Abstract

The invention relates to a separation and purification technology, and discloses an organic alcohol separation and purification method and application thereof. The method comprises the following steps: carrying out continuous chromatographic treatment I on a mixture containing organic alcohol and organic acid ester, and separating and recovering the organic alcohol; wherein a chromatographic filler adopted in the continuous chromatographic treatment I is homogeneous gel cation chromatographic resin. The organic alcohol obtained through the separation and purification method is high in purity and few in impurity, high-value recycling of the organic alcohol can be achieved, and energy consumption in the process is low.

Description

Technical Field

[0001] The invention relates to separation and purification technology, and in particular to a method for separation and purification of organic alcohol and application thereof. Background Art

[0002] 2,3-Butanediol is a colorless, odorless chiral compound with a boiling point of about 179-184°C and a high octane number. It is a potential high-value-added platform compound and is widely used in chemical, food, fuel and other fields. 2,3-Butanediol can be dehydrated to convert into the industrial solvent methyl ethyl ketone, which can be used as a fuel additive and a solvent in the resin and paint industries. Methyl ethyl ketone is further dehydrated to 1,3-butadiene, which can be used as a synthetic substrate for rubber products. In addition, 2,3-butanediol also shows potential application value in dyes, explosives, perfumes, drug carriers and other fields, but its high price hinders its application.

[0003] 1,3-Propanediol (PDO) is a colorless, odorless, salty, hygroscopic viscous liquid. It can be used as a raw material to produce cosmetics, drugs, coatings, etc. Its high molecular weight polymer synthesized as a monomer can be used in textiles, degradable plastics, engineering plastics and other fields. Due to the advantages of low cost, mild reaction conditions, renewable raw materials and low environmental pollution in the biological production of PDO, it has gradually become a hot topic of research. However, the fermentation process is accompanied by the production of by-products such as lactic acid, 2,3-butanediol, and acetic acid. Since the boiling point of 2,3-butanediol is lower than that of PDO (boiling point 210-211°C), 2,3-butanediol can be aggregated as a light component during the post-extraction distillation of PDO, and 2,3-butanediol accounts for a high proportion of the light components, about 40%. Directly dumping these light components not only pollutes the environment but also increases environmental protection costs. Therefore, separating 2,3-butanediol from the light components of PDO distillation can not only reduce environmental pollution and environmental pressure, but also increase the added value of light components.

[0004] However, the light components of PDO distillation contain not only 2,3-butanediol, but also low-boiling-point impurities such as lactic acid (122°C), 1,3-propylene glycol monoacetate (the boiling point is estimated to be about 160-180°C based on the accumulated PDO distillation data), and 1,2-propylene glycol (boiling point 184.8°C). In particular, the boiling points of 1,3-propylene glycol monoacetate and 2,3-butanediol are similar, and it is difficult to effectively separate the two using only vacuum distillation or vacuum distillation, while atmospheric distillation requires a higher temperature and has the problem of high energy consumption. Summary of the invention

[0005] The purpose of the present invention is to overcome the problems of the prior art in that 2,3-butanediol and 1,3-propylene glycol monoacetate in the light components of PDO distillation are difficult to separate by vacuum distillation and the energy consumption of atmospheric distillation is high, and to provide a method for separating and purifying an organic alcohol and its application. The organic alcohol obtained by the separation and purification method has high purity and few impurities, and can realize high-value recovery and utilization of the organic alcohol, and the process has low energy consumption.

[0006] In order to achieve the above-mentioned purpose, the first aspect of the present invention provides a method for separating and purifying organic alcohols, which method comprises: subjecting a mixture containing organic alcohols and organic acid esters to continuous chromatography treatment I to separate and recover the organic alcohols; wherein the chromatographic filler used in the continuous chromatography treatment I is a uniform particle gel cationic chromatographic resin.

[0007] Preferably, the uniform particle size gel cation chromatography resin has sulfonic acid groups loaded on its skeleton.

[0008] Preferably, the backbone of the uniform particle size gel cation chromatography resin contains styrene-divinylbenzene copolymer.

[0009] Preferably, the uniform particle size gel cation chromatography resin is LX1850 resin, S1850 resin or S1860 resin.

[0010] Preferably, the conditions of the continuous chromatography treatment I include: the eluent is water, the chromatographic column volume is 120-180 mL, the loading volume is 0.1-0.2 BV, the flow rate range of the eluent is 25-30 BV / h, and the temperature range is 35-45°C.

[0011] Preferably, when the mixture containing organic alcohols and organic acid esters also contains organic acid, the method further comprises: before performing the continuous chromatography treatment I, performing continuous chromatography treatment II on the mixture containing organic acid, organic alcohols and organic acid esters to separate and remove the organic acid from the mixture, and the chromatographic filler used in the continuous chromatography treatment II is a gel-type anion chromatography resin.

[0012] Preferably, the gel-type anion chromatography resin is S2850 resin or LXP-311 resin.

[0013] Preferably, the conditions of the continuous chromatography treatment II include: the eluent is water, the chromatographic column volume is 120-180 mL, the loading volume is 0.1-0.2 BV, the flow rate range of the eluent is 25-30 BV / h, and the temperature range is 35-45°C.

[0014] Preferably, the organic alcohol is a polyol, and the organic acid ester is an acetate of the polyol.

[0015] Preferably, the boiling point difference between the organic alcohol and the organic acid ester is 0-20°C.

[0016] Preferably, the mixture is a fraction obtained by distilling light components of 1,3-propanediol fermentation broth.

[0017] Preferably, the content of 1,3-propylene glycol in the distilled light components of the 1,3-propylene glycol fermentation broth is 40-60%, the content of 2,3-butylene glycol is 30-45%, and the content of 1,3-propylene glycol acetate and 2,3-butylene glycol acetate is 15-25%.

[0018] Preferably, the distillation conditions include: oil bath temperature of 80-85°C, system pressure <100Pa, reflux ratio of 2-10:1, more preferably 4-5:1;

[0019] Alternatively, the distillation conditions include: a bottom temperature of 95-115° C., a pressure of 250-300 Pa, and a reflux ratio of 1-10:1.

[0020] Preferably, the preparation process of the distillation light components of the 1,3-propylene glycol fermentation broth comprises: subjecting the 1,3-propylene glycol fermentation broth to membrane filtration (such as ceramic membrane filtration), evaporation concentration, primary distillation, and recovery of aggregated light components.

[0021] The second aspect of the present invention provides the use of the above method in separating and purifying 2,3-butanediol from the distillation light components of 1,3-propanediol fermentation broth.

[0022] Through the above technical scheme, the beneficial effects of the present invention are as follows: the uniform-particle gel cationic chromatographic resin is used for continuous chromatographic treatment, so that the organic alcohol and the organic acid ester in the mixture can be effectively separated; further, by combining the uniform-particle gel cationic chromatographic resin with the gel-type anion chromatographic resin, the organic alcohol can be effectively separated from the mixture containing the organic alcohol, the organic acid and the organic acid ester, and the obtained target organic alcohol has high purity, few impurities and high recovery rate, such as efficiently separating and extracting 2,3-butanediol from the distillation light components of 1,3-propanediol fermentation broth, realizing the high-value recovery and utilization of the target organic alcohol, and reducing environmental pollution and environmental protection pressure; the whole method process does not involve atmospheric distillation, and the energy consumption is low. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a diagram showing the separation effect of lactic acid and 2,3-butanediol in the distillation fraction of PDO light components by the S2850 chromatographic resin in Example 1, wherein the abscissa is the volume of the chromatographic effluent and the ordinate is the liquid content g / L;

[0024] Figure 2This is a diagram showing the separation effect of the LX1850 chromatographic column on 1,3-propylene glycol monoacetate and 2,3-butanediol in the distillation fraction of the PDO light component in Example 1, wherein the abscissa is the volume of the chromatographic effluent and the ordinate is the liquid content g / L. DETAILED DESCRIPTION

[0025] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0026] The first aspect of the present invention provides a method for separating and purifying organic alcohols, the method comprising: subjecting a mixture containing organic alcohols and organic acid esters to continuous chromatography treatment I to separate and recover the organic alcohols; wherein the chromatographic filler used in the continuous chromatography treatment I is a uniform particle gel cationic chromatographic resin.

[0027] During the research and development process, the inventors of the present invention unexpectedly discovered that when recycling organic alcohol based on a mixture containing organic alcohol and organic acid ester, a uniform-particle gel cationic chromatographic resin can be used to effectively adsorb the organic acid ester and other impurities that can be adsorbed by the uniform-particle gel cationic chromatographic resin in the mixture to obtain an eluent rich in organic alcohol; the organic alcohol separated by this process has high purity, few impurities, and a high recovery rate, which can achieve high-value recycling of organic alcohol.

[0028] The method provided by the present invention is obtained in the process of studying the distillation light components of 1,3-propylene glycol fermentation broth. After verification on different mixture systems, it is also applicable to the separation and purification of organic alcohols in other mixture systems containing organic alcohols and organic acid esters.

[0029] In the present invention, the uniform-particle gel cation chromatographic resin can utilize the polarity difference between organic alcohol and organic acid ester to remove impurity components such as organic acid ester in the mixture. Preferably, the skeleton of the uniform-particle gel cation chromatographic resin is loaded with sulfonic acid groups. In this preferred embodiment, the adsorption effect of the sulfonic acid groups is beneficial to improve the separation effect of organic alcohol and organic acid ester and other impurities in the mixture, and further improve the purity of the separated organic alcohol.

[0030] More preferably, the skeleton of the uniform particle size gel cation chromatography resin contains styrene-divinylbenzene copolymer.

[0031] Preferably, the uniform gel cation chromatographic resin is selected from at least one of a calcium-type uniform gel cation chromatographic resin, a sodium-type uniform gel cation chromatographic resin and a potassium-type uniform gel cation chromatographic resin, and more preferably a sodium-type uniform gel cation chromatographic resin. The inventors have found that under this preferred embodiment, the purity of the separated organic alcohol is improved.

[0032] Specifically, the uniform particle size gel cation chromatography resin can be LX1850 resin, S1850 resin or S1860 resin purchased from Xi'an Lanxiao Technology New Materials Co., Ltd.

[0033] According to the present invention, preferably, the conditions of the continuous chromatography treatment I include: the eluent is water, the volume of the chromatographic column is 120-180 mL, specifically 120 mL, 130 mL, 140 mL, 150 mL, 160 mL, 170 mL, 180 mL, or any value between the above two values; the sample volume is 0.1-0.2 BV, specifically 0.1 BV, 0.12 BV, 0.14 BV, 0.16 BV, 0.18 BV, 0.2BV, or any value between the above two values; the flow rate interval of the eluent is 25-30BV / h, specifically 25BV / h, 26BV / h, 27BV / h, 28BV / h, 29BV / h, 30BV / h, or any value between the above two values; the temperature interval is 35-45°C, specifically 35°C, 37°C, 39°C, 41°C, 43°C, 45°C, or any value between the above two values. During the continuous chromatography treatment I, the content of organic alcohol and organic acid ester in the eluent can be detected regularly, and the effluent is terminated when there is no organic acid ester in the effluent and the organic alcohol recovery amount is the highest; for example, every 0.08-0.15BV of the effluent is sampled to detect the content of organic alcohol and organic acid ester, which can be specifically detected by liquid chromatography.

[0034] In the present invention, if the mixture containing organic alcohol and organic acid ester may also contain organic acid, in this case, the method for separating and purifying organic alcohol further comprises: before the continuous chromatography treatment I, the mixture containing organic acid, organic alcohol and organic acid ester is subjected to continuous chromatography treatment II to separate the organic acid from the mixture to obtain the mixture containing organic alcohol and organic acid ester; wherein the chromatographic filler used in the continuous chromatography treatment II is a gel-type anion chromatography resin. The gel-type anion chromatography resin is used to effectively adsorb the organic acid and other impurities that can be adsorbed by the gel-type anion chromatography resin in the mixture, and the acidic substances in the mixture are allowed to flow out slowly to remove the organic acid, and then the mixture containing organic alcohol and organic acid ester is obtained by segmented collection (eluent substantially free of organic acid); and the mixture containing organic alcohol and organic acid ester is further subjected to continuous chromatography treatment I to separate and obtain organic alcohol.

[0035] It should be noted that the continuous chromatography treatment I and the continuous chromatography treatment II in the present invention are only used to distinguish two different chromatography treatment processes, and do not limit the order of the two.

[0036] In the present invention, the gel-type anion chromatography resin is an acid retardation chromatography resin, which can allow the acidic substances in the material to flow out slowly and remove impurity components such as organic acid components in the mixture. Preferably, the gel-type anion chromatography resin can be specifically S2850 resin or LXP-311 resin purchased from Xi'an Lanxiao Technology New Materials Co., Ltd.

[0037] According to the present invention, preferably, the conditions of the continuous chromatography treatment II include: the eluent is water, the volume of the chromatographic column is 120-180 mL, specifically 120 mL, 130 mL, 140 mL, 150 mL, 160 mL, 170 mL, 180 mL, or any value between the above two values; the sample volume is 0.1-0.2 BV, specifically 0.1 BV, 0.12 BV, 0.14 BV, 0.16 BV, 0.18 BV, 0.2BV, or any value between the above two values; the flow rate interval of the eluent is 25-30BV / h, specifically 25BV / h, 26BV / h, 27BV / h, 28BV / h, 29BV / h, 30BV / h, or any value between the above two values; the temperature interval is 35-45°C, specifically 35°C, 37°C, 39°C, 41°C, 43°C, 45°C, or any value between the above two values. During the continuous chromatography treatment II, the content of organic alcohol and organic acid in the eluent can be detected regularly, and the process is terminated when the effluent does not contain organic acid and the organic alcohol recovery amount is the highest; for example, the eluent is sampled every 0.08-0.15BV to detect the content of organic alcohol and organic acid, which can be specifically detected by liquid chromatography.

[0038] The method provided by the present invention can effectively separate organic alcohol from a mixture containing any organic alcohol, organic acid and organic acid ester. It should be particularly noted that the boiling point difference between the organic alcohol and the organic acid ester is 0-20°C. The method provided by the present invention can more effectively separate organic alcohol and organic acid ester with similar boiling points in the eluent after continuous chromatography treatment II, obtain organic alcohol with higher purity, effectively overcome the problem of difficulty in vacuum distillation separation of components with similar boiling points, and do not need to perform atmospheric distillation with high temperature and high energy consumption, effectively reducing energy consumption and cost.

[0039] In the present invention, the organic alcohol is a polyol, specifically an alcohol compound containing two or more hydroxyl groups (-OH), and may be an aliphatic polyol or an aromatic polyol, and may or may not have a substituent; preferably, an aliphatic polyol. Exemplarily, the organic alcohol in the mixture may be 1,3-propylene glycol or 2,3-butanediol, and more preferably 2,3-butanediol.

[0040] In the present invention, the organic acid ester may be a dehydration product of any organic carboxylic acid and a polyol. Preferably, the organic acid ester is an acetate of a polyol, wherein the polyol is 1,3-propylene glycol or 2,3-butylene glycol. Exemplarily, the organic acid ester may be at least one of 1,3-propylene glycol monoacetate, 2,3-butylene glycol diethyl ester and 1,3-propylene glycol diacetate.

[0041] In the present invention, the organic acid may be a monobasic acid or a polybasic acid, may or may not have other substituents; preferably, the organic acid is an acid having 3-6 carbon atoms, specifically propionic acid, malonic acid, n-butyric acid, 2-methylpropionic acid, succinic acid, n-valeric acid, 2-methylbutyric acid, 3-methylbutyric acid, tartaric acid, malic acid, lactic acid, citric acid, etc., more preferably lactic acid.

[0042] According to the present invention, the mixture may be derived from any chemical process capable of producing a mixture containing organic alcohols, organic acids and organic acid esters. Preferably, the mixture is a fraction obtained by distilling the light fraction of 1,3-propanediol fermentation broth (PDO light fraction for short). The mixture may be any fraction containing organic alcohols when the PDO light fraction is distilled, more preferably an intermediate fraction.

[0043] According to the present invention, preferably, the content of 1,3-propylene glycol in the PDO light component is 40-60%, the content of 2,3-butylene glycol is 30-45%, and the content of polyol acetate is 15-25%; wherein the polyol acetate is 1,3-propylene glycol acetate and / or 2,3-butylene glycol acetate, specifically at least one of 1,3-propylene glycol monoacetate, 2,3-butylene glycol diacetate and 1,3-propylene glycol diacetate.

[0044] According to the present invention, preferably, the distillation conditions include: oil bath temperature of 80-85°C, specifically 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, or any value between the above two values; system pressure <100Pa, specifically 5Pa, 20Pa, 40Pa, 60Pa, 80Pa, 90Pa, or any value between the above two values; reflux ratio of 2-10:1, specifically 10:1, 8:1, 5:1, 4:1, 3:1, 2:1, or any value between the above two values; more preferably 4-5:1. The distillation conditions are specifically suitable for laboratory or pilot stage.

[0045] According to the present invention, preferably, the distillation conditions include: the bottom temperature is 95-115°C, specifically 95°C, 100°C, 105°C, 110°C, 115°C, or any value between the above two values; the pressure is 250-300Pa, specifically 250Pa, 260Pa, 270Pa, 280Pa, 290Pa, 300Pa, or any value between the above two values; the reflux ratio is 1-10:1, specifically 10:1, 8:1, 4:1, 3:1, 2:1, 1:1, or any value between the above two values. The distillation conditions are specifically suitable for the industrial production stage.

[0046] According to the present invention, the PDO light component can be obtained by treating 1,3-propylene glycol fermentation broth by conventional methods. Preferably, the preparation process of the PDO light component comprises: subjecting the 1,3-propylene glycol fermentation broth to ceramic membrane filtration, evaporation concentration, and primary distillation, and collecting and gathering the light components to obtain the PDO light component.

[0047] The method for separating and purifying organic alcohols provided by the present invention can be used to separate and purify organic alcohols from any mixture containing organic alcohols, organic acids and organic acid esters, and the obtained organic alcohols have high purity and few impurities. Based on this, the second aspect of the present invention provides the use of the above method in separating and purifying 2,3-butanediol from the distillation light components of 1,3-propylene glycol fermentation broth.

[0048] According to a particularly preferred embodiment of the present invention, a method for separating and purifying 2,3-butanediol from the distillation light components of 1,3-propanediol fermentation broth comprises the following steps:

[0049] (1) distilling the PDO light component to obtain a mixture containing organic alcohol, organic acid and organic acid ester, contacting the mixture with a gel-type anion chromatographic resin to perform continuous chromatography treatment II to obtain a first eluent from which the organic acid is removed;

[0050] (2) contacting the first eluate with a uniform particle size gel cationic chromatographic resin to perform continuous chromatography treatment I to obtain a second eluate rich in organic alcohol;

[0051] The distillation conditions include: oil bath temperature of 80-85°C, system pressure <100Pa, reflux ratio of 2-10:1, the gel-type anion chromatographic resin is S2850 resin or LXP-311 resin; the uniform-particle gel cation chromatographic resin is LX1850 resin, S1850 resin or S1860 resin;

[0052] The conditions of the continuous chromatography treatment I and the continuous chromatography treatment II independently include: the eluent is water, the chromatographic column volume is 120-180mL, the sample volume is 0.1-0.2BV, the flow rate range of the eluent is 25-30BV / h, and the temperature range is 35-45°C; during the continuous chromatography treatment II, every 0.08-0.15BV of the eluent is sampled to detect the content of organic alcohol and organic acid, and every 0.08-0.15BV of the effluent is sampled to detect the content of organic alcohol and organic acid ester during the continuous chromatography treatment I.

[0053] The present invention will be described in detail below through examples.

[0054] In the following examples, the content of each component in the eluent was detected by gas chromatography, and the specific process was as follows:

[0055] 1. Gas chromatograph model: Agilent 8860;

[0056] 2. Chromatographic conditions

[0057] Chromatographic column: DB-624;

[0058] Temperature conditions: column temperature was maintained at 70°C for 2 min, then increased to 240°C at 20°C / min and maintained for 8 min, injection port temperature: 220°C;

[0059] FID detector temperature: 270°C, air flow: 100 ml / min, hydrogen flow: 10 ml / min, nitrogen flow: 25 ml / min; injection volume: 0.4 μL, diluent: methanol;

[0060] 3. Solution preparation

[0061] Standard: Pipette 500 μL of the standard into a test tube, add 50 μL of diluent and mix well (injection will give the main peak time of the spectrum);

[0062] Test solution: Pipette 500 μL of the filtered sample into a test tube, add 500 μL of diluent and mix well (injection gives the main peak area percentage content).

[0063] In the following embodiments, the preparation process of PDO light components is as follows: 1,3-propylene glycol fermentation broth is filtered through a ceramic membrane, evaporated and concentrated, and subjected to primary distillation, and PDO light components are extracted from the top of a distillation tower (dehydrogenation tower), which contains about 40% 1,3-propylene glycol, about 40% 2,3-butylene glycol, about 18% 1,3-propylene glycol monoacetate, and about 2% other unknown impurities.

[0064] Example 1

[0065] (1) The PDO light component was directly placed in a small-scale glass distillation tower and heated in an oil bath at 85°C. The system pressure was controlled at 90 Pa. The distillation was performed by changing the reflux ratio. The reflux ratios were 10:1, 8:1, 5:1, 4:1, 3:1, and 2:1, respectively. The relevant parameters of each fraction (mainly including gas phase purity and chromaticity) were detected. The results are shown in Table 1. When the reflux ratio was set to 4:1-5:1, the gas phase purity of 2,3-butanediol in the fraction was >80%, especially when the reflux ratio was 4:1, the gas phase purity of 2,3-butanediol could reach about 85%. The yield of 2,3-butanediol in the distillation with a gas phase purity of 70-85% was about 55%. The content of 1,3-propylene glycol monoacetate was high, about 13%, and contained a small amount of lactic acid, about 2-3%. The color of the fraction changed from yellow to colorless and transparent.

[0066] Table 1

[0067]

[0068] (2) The first chromatographic column was filled with S2850 chromatographic resin (purchased from Xi'an Lanxiao Technology New Materials Co., Ltd.), and the fractions after distillation with a reflux ratio of 4:1 (2,3-butanediol gas phase purity of about 85%) were collected and combined. After loading, water was used as an eluent to enter the first chromatographic column from the upper injection port (column volume was 150 mL, sample volume was 0.15 BV, flow rate was 28 BV / h, temperature was 40°C), and every 0.1 BV of the effluent was sampled and the sample was injected into the liquid phase to detect the content of lactic acid and 2,3-butanediol until the presence of lactic acid was detected. The first effluent before the detection sample was collected to obtain the first eluent without lactic acid to remove lactic acid. The separation effect diagram is shown in FIG. Figure 1 ;

[0069] (3) The second chromatographic column was filled with LX1850 chromatographic resin (purchased from Xi'an Lanxiao Technology New Materials Co., Ltd.). After the first eluent was loaded, water was used as the eluent from the upper injection port to enter the second chromatographic column (column volume was 150 mL, loading volume was 0.2 BV, flow rate was 30 BV / h, temperature was 45°C). Every 0.1 BV of the effluent was sampled and the sample was injected into the liquid phase to detect the content of 2,3-butanediol and 1,3-propylene glycol monoacetate until the presence of 1,3-propylene glycol monoacetate was detected. The first effluent before the detection sample was collected to obtain the second eluent. The separation effect diagram is shown in FIG. Figure 2 .

[0070] Before the chromatographic effluent of the second chromatographic column reaches 1BV, 2,3-butanediol and 1,3-propylene glycol monoacetate can be effectively separated, and the gas phase purity of 2,3-butanediol in the obtained second eluent is 96%, and the overall recovery rate of 2,3-butanediol in the PDO light component is about 85%, which proves that the method provided by the present invention can effectively separate and recover 2,3-butanediol from the PDO light component to obtain high-yield and high-purity 2,3-butanediol.

[0071] Example 2

[0072] (1) The PDO light component was directly placed in a small-scale glass distillation tower, heated in an oil bath at 80°C, the system pressure was controlled at 80 Pa, and distilled at a reflux ratio of 4:1. The gas phase purity of 2,3-butanediol in the obtained fraction was 73%, the content of 1,3-propylene glycol monoacetate was 21%, and the content of lactic acid was 6%;

[0073] (2) The first chromatographic column was filled with S2850 chromatographic resin (purchased from Xi'an Lanxiao Technology New Materials Co., Ltd.), the fractions after distillation were collected and combined, and water was used as the eluent from the upper injection port of the first chromatographic column after loading (column volume was 120 mL, loading volume was 0.1 BV, flow rate was 25 BV / h, temperature was 35°C), and every 0.08 BV of the effluent was sampled, and the sample was injected into the liquid phase to detect the content of lactic acid and 2,3-butanediol until the presence of lactic acid was detected, and the first effluent before the detection sample was collected to obtain the first eluent without lactic acid to remove lactic acid;

[0074] (3) The second chromatographic column was filled with S1860 chromatographic resin (purchased from Xi'an Lanxiao Technology New Materials Co., Ltd.), and the first eluent was loaded and then introduced into the second chromatographic column from the upper injection port using water as the eluent (column volume was 120 mL, loading volume was 0.1 BV, flow rate was 25 BV / h, temperature was 35°C), and every 0.08 BV of the effluent was sampled and the sample was injected into the liquid phase to detect the content of 2,3-butanediol and 1,3-propylene glycol monoacetate until the presence of 1,3-propylene glycol monoacetate was detected, and the first effluent before the detection sample was collected to obtain the second eluent.

[0075] The gas phase purity of 2,3-butanediol in the obtained second eluate is 94%, and the overall recovery rate of 2,3-butanediol in the PDO light component is about 78%.

[0076] Example 3

[0077] The separation and purification of 2,3-butanediol in the PDO light fraction was carried out according to the method of Example 2, except that the second chromatographic column was filled with S1850 chromatographic resin (purchased from Xi'an Lanxiao Technology New Materials Co., Ltd.), and the gas phase purity of 2,3-butanediol in the obtained second eluent was 93%, and the overall recovery rate of 2,3-butanediol in the PDO light fraction was about 73%.

[0078] Example 4

[0079] The separation and purification of 2,3-butanediol in the PDO light fraction was carried out according to the method of Example 1, except that the first chromatographic column was filled with LXP-311 chromatographic resin (purchased from Xi'an Lanxiao Technology New Materials Co., Ltd.), and the gas phase purity of 2,3-butanediol in the obtained second eluent was 95%, and the overall recovery rate of 2,3-butanediol in the PDO light fraction was about 80%.

[0080] Example 5

[0081] The separation and purification of 2,3-butanediol in the PDO light fraction was carried out according to the method of Example 3, except that the first chromatographic column was filled with LXP-311 chromatographic resin (purchased from Xi'an Lanxiao Technology New Materials Co., Ltd.), and the gas phase purity of 2,3-butanediol in the obtained second eluent was 91%, and the overall recovery rate of 2,3-butanediol in the PDO light fraction was about 70%.

[0082] Comparative Example 1

[0083] The separation and purification of 2,3-butanediol in the PDO light component was carried out according to the method of Example 2, except that the fraction after the distillation of the PDO light component was directly separated by macroporous adsorption resin DM130 (purchased from Ningbo Zhengguang Resin Co., Ltd.);

[0084] The gas phase purity of 2,3-butanediol in the stripped liquid was 81%, and the overall recovery rate of 2,3-butanediol in the PDO light component was about 20%, and the separation effect was not ideal.

[0085] Comparative Example 2

[0086] The separation and purification of 2,3-butanediol in the PDO light fraction was carried out according to the method of Example 2, except that the S2850 chromatographic resin was replaced by a macroporous adsorption resin SD300 (purchased from Ningbo Zhengguang Resin Co., Ltd.), and the S1860 chromatographic resin was replaced by a macroporous adsorption resin SD333 (purchased from Ningbo Zhengguang Resin Co., Ltd.);

[0087] The gas phase purity of 2,3-butanediol in the obtained second eluate is about 85%, and the overall recovery rate of 2,3-butanediol in the PDO light component is about 47%.

[0088] Comparative Example 3

[0089] The PDO light component was directly placed in a small test glass distillation tower and heated in an oil bath at 95-100°C. The system pressure was controlled at 80Pa, and distillation was performed by changing the reflux ratio (10:1, 8:1, 5:1, 4:1, 3:1, 2:1); the relevant parameters of each fraction were tested, mainly including gas phase purity and chromaticity. It was found that under this condition, only a small amount of high-boiling-point heavy components such as PDO in the original light component could be removed, and a large amount of low-boiling-point substances such as 1,3-propylene glycol monoacetate and lactic acid still existed. The gas phase purity of acetic acid could only reach more than 60%, but the color of the fraction changed from yellow to colorless and transparent.

[0090] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for separating and purifying an organic alcohol, characterized in that: The method includes: The mixture containing organic alcohol and organic acid ester is subjected to continuous chromatography treatment I to separate and recover the organic alcohol; wherein the chromatographic filler used in the continuous chromatography treatment I is a uniform particle gel cationic chromatographic resin.

2. The method according to claim 1, characterized in that The skeleton of the uniform particle size gel cation chromatography resin is loaded with sulfonic acid groups; Preferably, the backbone of the homogeneous gel cation chromatography resin contains styrene-divinylbenzene copolymer; Preferably, the uniform particle size gel cation chromatography resin is LX1850 resin, S1850 resin or S1860 resin.

3. The method according to claim 1, characterized in that The conditions of the continuous chromatography treatment I include: the eluent is water, the chromatographic column volume is 120-180 mL, the sample volume is 0.1-0.2 BV, the flow rate range of the eluent is 25-30 BV / h, and the temperature range is 35-45°C.

4. The method according to any one of claims 1 to 3, characterized in that When the mixture containing organic alcohol and organic acid ester also contains organic acid, the method further comprises: before the continuous chromatography treatment I, performing continuous chromatography treatment II on the mixture containing organic acid, organic alcohol and organic acid ester to separate and remove the organic acid from the mixture; Wherein, the chromatographic filler used in the continuous chromatography treatment II is a gel-type anion chromatography resin.

5. The method according to claim 4, characterized in that The gel-type anion chromatography resin is S2850 resin or LXP-311 resin; Preferably, the conditions of the continuous chromatography treatment II include: the eluent is water, the chromatographic column volume is 120-180 mL, the loading volume is 0.1-0.2 BV, the flow rate range of the eluent is 25-30 BV / h, and the temperature range is 35-45°C.

6. The method according to any one of claims 1 to 3, characterized in that: The organic alcohol is a polyol, and the organic acid ester is an acetate of the polyol; Preferably, the boiling point difference between the organic alcohol and the organic acid ester is 0-20°C.

7. The method according to claim 6, characterized in that The mixture containing organic alcohols and organic acid esters is a fraction obtained by distilling light components of 1,3-propylene glycol fermentation broth; Preferably, the content of 1,3-propylene glycol in the distilled light components of the 1,3-propylene glycol fermentation broth is 40-60%, the content of 2,3-butylene glycol is 30-45%, and the content of acetate of polyol is 15-25%; wherein the acetate of polyol is acetate of 1,3-propylene glycol and / or acetate of 2,3-butylene glycol.

8. The method according to claim 7, characterized in that The distillation conditions include: oil bath temperature of 80-85°C, system pressure <100Pa, reflux ratio of 2-10:1, more preferably 4-5:1; Alternatively, the distillation conditions include: a bottom temperature of 95-115° C., a pressure of 250-300 Pa, and a reflux ratio of 1-10:

1.

9. The method according to claim 7, characterized in that: The preparation process of the distillation light components of the 1,3-propylene glycol fermentation broth comprises: subjecting the 1,3-propylene glycol fermentation broth to membrane filtration, evaporation concentration, and primary distillation, and recovering the aggregated light components.

10. Use of the method according to any one of claims 1 to 9 in separating and purifying 2,3-butanediol from the distilled light components of 1,3-propanediol fermentation broth.

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