CN111909123A - Method and device for continuously separating and purifying 5-hydroxymethylfurfural and derivatives thereof - Google Patents
Method and device for continuously separating and purifying 5-hydroxymethylfurfural and derivatives thereof Download PDFInfo
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Abstract
The invention provides a method for continuously separating and purifying 5-hydroxymethyl furfural and derivatives thereof from a solution after saccharide dehydration, which comprises the following steps: using the solution obtained after preparing 5-hydroxymethylfurfural and derivatives thereof by saccharide dehydration as feed liquid of continuous chromatography, eluting by using eluent composed of weak-polarity and medium-strong-polarity organic solvents, and collecting fractions of 5-hydroxymethylfurfural and derivatives thereof. The method has the advantages of high separation purity, continuous process, small organic solvent consumption, simple operation and little environmental pollution.
Description
Technical Field
The invention relates to a method for purifying 5-hydroxymethylfurfural and derivatives thereof, in particular to a method for continuously separating and purifying 5-hydroxymethylfurfural and derivatives thereof from a solution after saccharide dehydration.
Background
5-Hydroxymethylfurfural (HMF) is an important platform compound, HMF molecules contain furan rings, hydroxyl groups, aldehyde groups and the like with high activity, and can be further converted through processes such as hydrogenation, esterification, halogenation, polymerization, hydrolysis and the like, so that the HMF has important potential application value in the fields of monomer synthesis, macrocyclic compound synthesis raw materials, pharmaceutical and pesticide intermediates and the like of high polymer materials, and simultaneously, the HMF purity is also required. Because HMF is mainly obtained by dehydrating and converting hexose and has low purity, the subsequent application is influenced, and therefore, the establishment of the high-purity 5-HMF separation and purification technology has important medical, social and economic values.
5-HMF is obtained from a hexose by catalytic dehydration, and when the reaction solvent is allowed to react with 5-HMF, the corresponding derivative of 5-HMF is formed, for example, when the reaction solvent is methanol, 5-hydroxymethylfurfural glycol acetal is formed.
The reaction system after the dehydration of the hexose contains various impurities such as formic acid, levulinic acid, humins and the like besides HMF and derivatives thereof, and the impurities are similar to one or more properties such as melting point, boiling point, polarity and the like of HMF and derivatives thereof, so that the impurities are difficult to separate.
At present, the separation and purification methods of HMF and its derivatives mainly include extraction, recrystallization, column chromatography, and distillation under reduced pressure. The extraction process is complex, repeated steps are needed, and the yield and purity of the HMF are low. Recrystallization requires a full-scale operation at low temperature, is energy intensive, and is difficult to remove impurities close to HMF solubility.
Chinese patent CN 105753819 a discloses a method for purifying HMF by using a chromatography column, which can obtain HMF crystals with high purity, but the raw material used in the method is commercially available HMF, i.e. HMF that has undergone a previous purification process.
US 4740605 discloses a method for separating and purifying HMF by ion exchange, which uses a solution obtained by acid homogeneous catalysis of fructose dehydration in an aqueous solution as a raw material, and separates the solution under a strong acid condition by ion exchange chromatography to obtain a concentrated aqueous HMF solution. The reduced pressure distillation process typically requires the HMF to be at a high temperature above 100 ℃ for a long period of time, also introducing other impurities during the separation process due to poor thermal stability. Although column chromatography is a common method for obtaining high-purity organic matter by purification, good separation of HMF cannot be achieved according to the solvent combination of the currently common packing and eluent. And the existing HMF separation methods are all intermittent processes, so that industrial scale-up is difficult.
Therefore, there is a need to develop a new method for direct and continuous separation and purification from the solution after the HMF and its derivatives are prepared by sugar dehydration reaction.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for continuously separating and purifying HMF and derivatives thereof from a solution obtained after sugar dehydration, which has the advantages of simple operation, continuous process, large treatment capacity, small organic solvent consumption, high product purity and small environmental pollution.
The invention also provides a device for continuously separating and purifying the HMF and the derivatives thereof from the solution after sugar dehydration.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for continuously separating and purifying 5-hydroxymethylfurfural and derivatives thereof comprises the following steps: adding a solution obtained after 5-hydroxymethylfurfural and derivatives thereof are prepared by saccharide dehydration into a continuous chromatographic column filled with a filler as a feed liquid, eluting by using an eluent composed of a weak-polarity organic solvent and a medium-strong-polarity organic solvent, and collecting fractions of HMF and/or derivatives thereof.
The structure of the 5-hydroxymethylfurfural and the derivative thereof is as follows:
wherein R is1May be H or C1-C4 alkyl, e.g. -CH3，-CH2CH3，-CH2CH2CH3， R2May be a C1-C4 acetal group, for example
And so on.
The saccharide is monosaccharide or polysaccharide containing six-carbon sugar basic structural unit, and comprises one or more of glucose, fructose, maltose, sucrose, inulin, starch, galactose, cellobiose, cellulose, oligo-glucose, anhydroglucose, etc.
The filler is silica gel, magnesium oxide, Florisil, alumina or titanium dioxide, preferably silica gel or alumina. The specification of the filler is 200-300 meshes. The filler can be added into a weak polar solvent before column filling, stirred into a slurry state and then filled into a column. The weight ratio of the filler to the feed liquid is 10:1 to 100:1, preferably 20:1 to 50: 1. The feeding method is that the organic phase is directly loaded by a wet method, namely, the feeding liquid is added into a chromatographic column after being concentrated or directly added into the chromatographic column.
The weak polar organic solvent is a slightly soluble or insoluble solvent with the polarity of less than 4.1 and/or the solubility of 5-hydroxymethylfurfural and derivatives thereof of less than 0.2g, such as one or more of n-hexane, petroleum ether, chloroform, cyclohexane, dichloromethane and the like, preferably petroleum ether and chloroform, and further preferably petroleum ether.
The medium-strong polar organic solvent is an organic solvent with the polarity of 4.3-6.0 and is mutually soluble with the weak polar solvent, such as ethyl acetate, acetone, ethanol and the like, preferably acetone and/or ethanol, and more preferably ethanol.
The volume ratio of the weak polar organic solvent to the medium strong polar organic solvent is 5:1-50:1, preferably 10:1-35: 1.
The aspect ratio of the chromatography column may be 2:1 to 20:1, preferably 4:1 to 6: 1.
The method can use a plurality of chromatographic columns for continuous circulating operation, preferably every 3-4 chromatographic columns are taken as a circulating unit, and components in the last chromatographic column are collected.
An apparatus for continuously separating and purifying HMF and derivatives thereof, comprising: the eluent storage tank is installed on the plurality of chromatographic columns on the rotary disc, the feed liquid storage tank, the product storage tank, the impurity storage tank, the control and drive system, pipelines for conveying eluent to the chromatographic columns, pipelines for conveying eluent among the chromatographic columns, pipelines for conveying feed liquid to the chromatographic columns, product output pipelines and impurity output pipelines.
Wherein, the filler in the chromatographic column is silica gel, magnesia, Florisil, alumina or titanium dioxide, and preferably silica gel or alumina. The specification of the filler is 200-300 meshes.
Wherein no regeneration and cleaning operation unit is required in the apparatus.
The invention adopts continuous chromatography to separate and purify 5-hydroxymethyl furfural and derivatives thereof from the solution after sugar dehydration, thereby obtaining unexpected separation effect. The skilled person generally thinks that when the continuous chromatography is used for separating and purifying organic mixtures, the elution solvent should be completely miscible with the target organic substance to be purified to achieve good separation effect, but the inventors of the present application have surprisingly found that the selection of a weakly polar solvent that is poorly soluble in HMF and its derivatives is more beneficial to rapidly remove the weakly polar impurities in the liquid to be separated. Meanwhile, a medium-strong polar solvent which can dissolve the HMF and the derivatives thereof and is mutually soluble with the weak polar solvent is selected, so that on one hand, the HMF and the derivatives thereof can be ensured to be in a dissolved state, a chromatographic column cannot be blocked, and on the other hand, the polar solvent and the filler have different interaction forces with the HMF, the derivatives thereof and impurities respectively, so that the separation of the HMF, the derivatives thereof and the polar impurities can be realized. When the polarity of the polar solvent is too strong, such as methanol, the miscibility with the non-polar solvent is poor, and when the polarity is weak, it is difficult to elute HMF and its derivatives from the column.
Compared with the prior art, the invention has the following characteristics and advantages: (1) the elution phase consisting of the weak polar solvent and the medium and strong polar solvent which are immiscible with the HMF and the derivatives thereof can realize the optimal separation effect on the HMF and the derivatives thereof, has high separation purity and no tailing, and ensures that the whole process is simple to operate and can be realized at normal temperature. The elution solvent has low toxicity, small dosage and little environmental pollution; (2) the whole separation process is carried out in an organic phase, so that side reactions of HMF and derivatives thereof can be effectively prevented; (3) the organic solution of HMF and the derivatives thereof is obtained by continuous chromatographic separation, the boiling point of the solvent is low, and the solvent is convenient to remove so as to obtain HMF and the derivatives thereof crystals; (4) the chromatographic column does not need to be regenerated and cleaned, the number of the chromatographic columns occupied by one operation cycle is greatly reduced, and the treatment capacity is higher under the same chromatographic column condition. (5) The separation process is continuous operation and can be directly and industrially amplified.
Drawings
FIG. 1 is a schematic diagram of a preferred embodiment of the continuous separation apparatus of the present invention, which includes only 1 separation cycle, and there may be a plurality of actual apparatuses. Which comprises the following steps: eluent reservoir 1, columns 2, 3 and 4 (the numbers here indicate the position of the columns and do not represent the columns themselves), feed solution reservoir 5, product reservoir 6 and impurity reservoir 7, line 2 for conveying eluent to the columns, lines 9 and 10 for conveying liquid between the columns, line 11 for conveying feed solution to the columns, product outlet line 13 and impurity outlet line 12.
The chromatographic column moves on the turntable from right to left, and the position of the feeding and discharging liquid is unchanged and does not move along with the chromatographic column.
Detailed Description
For the convenience of understanding the present invention, the present invention will be described below with reference to examples, which are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
In the examples, the contents of HMF and its derivatives in the effluent were qualitatively determined by silica gel thin layer chromatography (part 2010 pharmacopoeia), and the purity of HMF and its derivatives was analyzed by HPLC.
Example 1
Adding 5L (the content of HMF is 15 percent and the content of 5-hydroxymethylfurfural diacetal is 12 percent) of the reacted organic phase into a raw material tank of continuous chromatography, adding the mixture into a continuous chromatographic column filled with 10L of silica gel at the speed of 300ml/h, eluting with cyclohexane/ethyl acetate of 10:1, taking every four chromatographic columns as a circulating unit, collecting components in the two subsequent chromatographic columns to respectively obtain organic solutions containing purified HMF and 5-hydroxymethylfurfural diacetal, recovering the solvent to obtain 32.98g of HMF and 26.6g of 5-hydroxymethylfurfural diacetal per hour on average, and analyzing the purity of the HMF by High Performance Liquid Chromatography (HPLC) to be 87.3 percent, the yield to be 80.0 percent, the purity of the 5-hydroxymethylfurfural diacetal to be 92.1 percent and the yield to be 84.9 percent.
Example 2
Adding 5L (25% of HMF) of the reacted organic phase into a raw material tank of a continuous chromatographic column, adding the mixture into a chromatographic column filled with 10L of silica gel at the speed of 200ml/h, eluting with petroleum ether/ethanol (30: 1), taking every three chromatographic columns as a circulating unit, collecting components in the next chromatographic column to obtain an organic solution containing purified HMF, recovering the solvent, and obtaining 41.7g of HMF per hour on average, wherein the purity of the HMF is 99.6% by HPLC analysis and the yield is 92.3%.
Example 3
5L of the reacted organic phase (25% HMF) was taken and added to a feed tank for continuous chromatography, 400ml/h was added to a column containing 12L of alumina, elution was carried out with chloroform/acetone 25:1, every three columns were used as a circulation unit, the fractions in the latter column were collected to give an organic solution containing purified HMF, and 85.8g of HMF was obtained per hour on average, with an HMF purity of 95.6% by HPLC analysis and a yield of 91.2% by recovery of the solvent.
Example 4
5L of reacted organic phase (25% HMF) was taken and added to a feed tank for continuous chromatography, and added to a column containing 8L of titanium dioxide at a rate of 300ml/h, eluted with 20:1 dichloromethane/ethanol, with every three columns being a recycle unit, and the fractions in the latter column were collected to give an organic solution containing purified HMF, and the solvent was recovered to give 62.7g of HMF with an HPLC assay HMF purity of 96.2% and a yield of 89.5%.
Comparative example 1
Adding 5L (HMF content is 25%) of organic phase after reaction into a raw material tank of a continuous chromatographic column, adding into a chromatographic column filled with 10L of silica gel at the speed of 200ml/h, eluting with petroleum ether, and taking ten chromatographic columns as a circulating unit, so that a product cannot be obtained.
Comparative example 2
Adding 5L (HMF content is 25%) of the reacted organic phase into a raw material tank of a continuous chromatographic column, adding the organic phase into a chromatographic column filled with 10L of silica gel at a speed of 200ml/h, eluting with ethanol, taking every three chromatographic columns as a circulating unit, collecting components in the next chromatographic column to obtain an organic solution containing purified HMF, recovering the solvent, and obtaining 51.4g of HMF per hour on average, wherein the HMF purity is 84.5% by HPLC analysis and the yield is 96.6%.
Comparative example 3
Adding 5L (25% of HMF) of the reacted organic phase into a raw material tank of a continuous chromatographic column, adding the mixture into a chromatographic column filled with 10L of weakly acidic polystyrene cation exchange resin at the speed of 200ml/h, eluting the mixture by using petroleum ether/ethanol (30: 1), taking every five chromatographic columns as a circulating unit, collecting components in the next chromatographic column to obtain an organic solution containing the HMF, recovering the solvent, and obtaining 16.6g of HMF per hour on average, wherein the purity of the HMF is 92.4% by HPLC analysis, and the yield is 34.1%.
Claims (12)
1. A method for continuously separating and purifying 5-hydroxymethylfurfural and derivatives thereof comprises the following steps: adding a solution obtained after 5-hydroxymethylfurfural and derivatives thereof are prepared by saccharide dehydration into a continuous chromatographic column filled with a filler as a feed liquid, eluting by using an eluent composed of a weak-polarity organic solvent and a medium-strong-polarity organic solvent, and collecting fractions of HMF and/or derivatives thereof.
2. The method of claim 1, wherein the 5-hydroxymethylfurfural and derivatives thereof have the structure:
wherein R is1Is H or C1-C4 alkyl, R2Is a C1-C4 acetal group.
3. The method of claim 1, wherein the filler is one or more of silica gel, magnesia, Florisil, alumina, and titanium dioxide.
4. The method according to claim 1, wherein the filler is stirred with the weakly polar solvent into a slurry and then packed into the column.
5. The process according to claim 1, wherein the weakly polar organic solvent is a sparingly or poorly soluble solvent having a polarity of less than 4.1 and/or a solubility of less than 0.2g for 5-hydroxymethylfurfural and its derivatives.
6. The method according to claim 1, wherein the low-polarity organic solvent is one or more selected from n-hexane, petroleum ether, chloroform, cyclohexane and dichloromethane.
7. The method according to claim 1, wherein the medium-strong polar organic solvent is an organic solvent with a polarity of 4.3-6.0 and is miscible with the weak polar solvent.
8. The method according to claim 1, wherein the medium-strong polar organic solvent is one or more selected from ethyl acetate, acetone and ethanol.
9. The process according to claim 1, wherein the volume ratio of the weakly polar and the moderately strongly polar organic solvent is from 5:1 to 30:1, preferably from 10:1 to 20: 1.
10. An apparatus for continuously separating and purifying 5-hydroxymethylfurfural and derivatives thereof, which comprises: the eluent storage tank is installed on the chromatographic column on the rotary table, the feed liquid storage tank is installed on the rotary table, the product storage tank is installed on the rotary table, the impurity storage tank is installed on the rotary table, the control and driving system is installed on the rotary table, the eluent storage tank is installed on the rotary.
11. The apparatus of claim 10, wherein the packing material in the chromatographic column is silica gel, magnesia, florisil, alumina or titania.
12. The apparatus of claim 10, wherein the apparatus is free of regeneration and cleaning operations.
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| CN101386611A (en) * | 2007-09-14 | 2009-03-18 | 中国科学院大连化学物理研究所 | Method for preparing 5-hydroxymethyl-furfural |
| US20140288298A1 (en) * | 2011-11-30 | 2014-09-25 | Oji Holdings Corporation | Method for manufacturing monosaccharides, oligosaccharides, and furfurals from biomass |
| WO2017184545A1 (en) * | 2016-04-18 | 2017-10-26 | Rennovia, Inc. | Conversion of fructose-containing feedstocks to hmf-containing product |
| CN110143936A (en) * | 2018-02-12 | 2019-08-20 | 中国石油化工股份有限公司 | A method of 5 hydroxymethyl furfural is isolated and purified in solution after carbohydrate dehydration |
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- 2019-05-07 CN CN201910373711.6A patent/CN111909123A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN201076777Y (en) * | 2007-06-14 | 2008-06-25 | 山东福田药业有限公司 | Subsequent type stimulant moving bed |
| CN101386611A (en) * | 2007-09-14 | 2009-03-18 | 中国科学院大连化学物理研究所 | Method for preparing 5-hydroxymethyl-furfural |
| US20140288298A1 (en) * | 2011-11-30 | 2014-09-25 | Oji Holdings Corporation | Method for manufacturing monosaccharides, oligosaccharides, and furfurals from biomass |
| WO2017184545A1 (en) * | 2016-04-18 | 2017-10-26 | Rennovia, Inc. | Conversion of fructose-containing feedstocks to hmf-containing product |
| CN110143936A (en) * | 2018-02-12 | 2019-08-20 | 中国石油化工股份有限公司 | A method of 5 hydroxymethyl furfural is isolated and purified in solution after carbohydrate dehydration |
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