CN112574228B - Method for separating isosorbide - Google Patents
Method for separating isosorbide Download PDFInfo
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- CN112574228B CN112574228B CN201910934826.8A CN201910934826A CN112574228B CN 112574228 B CN112574228 B CN 112574228B CN 201910934826 A CN201910934826 A CN 201910934826A CN 112574228 B CN112574228 B CN 112574228B
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Abstract
The invention discloses a method for separating isosorbide. The solid acid is used for catalyzing sorbitol to dehydrate to prepare reaction liquid, and then the reaction liquid is separated and purified to obtain the isosorbide. The separation and purification process uses isopropanol for elution, during separation, the carbonization degree of a substrate subjected to reduced pressure distillation is not high, the carbonized product is dissolved in water and is easy to elute, the treatment and discharge of eluent are simple, and the used high-boiling-point solvent can be recycled and accords with green chemistry; during purification, the process is simple, the consumed time is short, and raw materials and solvents are not wasted to a great extent; high yield and high product purity.
Description
Technical Field
The invention relates to the field of chemical separation, in particular to a method for separating isosorbide.
Background
Sorbitol is derivatized through dehydration and hydrogenolysis to obtain a series of high-value-added bio-based chemicals, and isosorbide is diol derivatized through secondary dehydration of sorbitol.
The compound is used as a bio-based platform compound, has application in many fields based on the special structural characteristics (rigid molecular structure and chiral center) of the compound, can be used as a substitute of a plurality of petroleum compounds, has wide sorbitol source, and has important significance in the context of green chemistry. Isosorbide has been used in many synthetic applications to date, for example isosorbide dinitrate has been used as a vasodilator for decades; isosorbide dimethyl ether is used as a solvent in cosmetics; isosorbide diesters are used as surfactants and PVC plasticizers; producing polycarbonates, epoxies, polyesters, polyamides, and the like. The yield of isosorbide is relatively low in China, and the reasons are as follows: the downstream market is not completely opened, and the application range is wide but the scale is not large; because of numerous dehydration products of sorbitol, the development of the catalyst for preparing isosorbide by sorbitol dehydration is difficult to break through, and the subsequent separation process is complex and takes long time, and has the problems of inevitable resource waste, environmental pollution and the like, which directly causes the increase of the production cost and also does not meet the requirement of green chemistry.
Aiming at the defects of isosorbide production, a plurality of scientific researchers report the research on the separation and purification of a catalyst and isosorbide related to the preparation of isosorbide by dehydrating sorbitol, and domestic patents on the separation and purification of isosorbide are few, the process is complicated, and the operability is poor.
Chinese patent CN102757445A discloses a preparation process of isosorbide, which comprises the following process steps: dehydration reaction, neutralization and decoloration, electrodialysis desalination, concentration and dehydration, extraction crystallization, freeze drying, quality inspection and packaging. Although the method avoids the high-temperature distillation process, the separation process is complicated, and the operability for mass production is not strong.
Chinese patent CN103980286A discloses a method for continuously producing isosorbide and a device used by the same, the method comprises: feeding, reacting, condensing and separating. The process of the method is simple, but the reaction and the separation are only continuous in a continuous way instead of a practical continuous way, and the process has the defects that the equipment and the device after the reaction are very troublesome to handle, particularly the elution of coke materials prolongs the production period of the isosorbide, the purity of the isosorbide is not high, and further purification is needed, which is not favorable for the production.
Chinese patent CN201611092777.0 discloses a method for preparing isosorbide, which comprises the steps of reaction, decolorization ion exchange, concentration, crystallization, centrifugation, secondary crystallization and the like. Although the obtained product has high purity, the method has too many separation and purification processes and complex process.
Disclosure of Invention
Aiming at the defects in the engineering practice, the invention provides a method for separating and purifying isosorbide reaction liquid, which solves the problems of serious substrate carbonization, difficult elution, low yield, long time consumption, environmental pollution and the like in the prior art when the isosorbide is separated and purified.
The method for separating and purifying the isosorbide has the advantages of low substrate carbonization degree, easiness in elution, very simple process, high yield, environmental friendliness, strong operability and the like in the separation and purification process, and has important application value when being used for separating and purifying the isosorbide.
The invention aims to provide a method for separating isosorbide, which comprises the following steps:
s1, mixing the isosorbide reaction liquid to be separated with high boiling point substances, and distilling to obtain a fraction;
s2, dissolving the distillate by using a solvent, cooling and recrystallizing; carrying out primary filtration to obtain a first solid and a first filtrate;
and S3, adding an adsorbent into the first filtrate, then carrying out secondary filtration to obtain a second filtrate, and separating the second filtrate to obtain a second solid.
According to some embodiments of the invention, the high boiling point material is a polar material with a boiling point above 600 ℃.
According to some embodiments of the invention, the high boiling point material is polypropylene glycol.
According to some embodiments of the invention, the high boiling point material is polypropylene glycol 2000.
According to some embodiments of the invention, the solvent is selected from one or more of ethyl acetate, isopropanol and ethanol.
According to some embodiments of the invention, the adsorbent is selected from one or more of activated carbon, alumina and silica gel.
According to some embodiments of the invention, the distillation is a vacuum distillation.
According to some embodiments of the invention, the first filtration is a reduced pressure filtration.
According to some embodiments of the invention, the separation is rotary evaporation.
According to some embodiments of the present invention, the high boiling point substance added in the S1 step is 50% -300% of the isosorbide reaction solution to be separated on a w/w basis.
According to some embodiments of the present invention, the high boiling point substance added in the S1 step is 100% -250% of the isosorbide reaction solution to be separated on a w/w basis.
According to some embodiments of the invention, the solvent in step S2 is 100% to 1500% of the fraction on a v/w basis.
According to some embodiments of the invention, in the step S2, the solvent is 150% to 500% of the fraction in v/w;
according to some embodiments of the invention, the activated carbon added in step S3 is 5-200% of the primary filtrate on a w/v basis.
According to some embodiments of the invention, the activated carbon added in step S3 is 10-100% of the first filtrate on a w/v basis.
According to some embodiments of the invention, the temperature of the mixing is 100-300 ℃.
According to some embodiments of the invention, the temperature of the mixing is 150-.
According to some embodiments of the invention, in the S1 step, the temperature of the distillation is 40 to 60 ℃ below the boiling point of the high boiling point solution;
according to some embodiments of the invention, the temperature of the dissolution with the solvent in the S2 step is 25-70 ℃;
according to some embodiments of the invention, in the step S2, the recrystallization condition is to stand at-15 to 0 ℃ for 1 to 12 hours.
According to some embodiments of the present invention, in the step of S2, the recrystallization is performed by first standing at 1-5 ℃ for 0.5-12 hours and then at-15 to-5 ℃ for 0.5-12 hours.
According to some embodiments of the invention, the recrystallization is repeated to equal to or greater than a specified purity.
According to some embodiments of the invention, the recrystallization is repeated to a specified purity, the purity being 96-99%.
According to some embodiments of the present invention, the isosorbide reaction solution is a reaction solution for preparing isosorbide by dehydration of sorbitol after recovering the solid acid catalyst.
According to some embodiments of the invention, further comprising a pretreatment step of washing the isosorbide reaction solution with a washing solution; the washing liquid is one or more of isopropanol, ethyl acetate and propanol.
According to some embodiments of the invention, the wash solution is isopropanol.
According to some embodiments of the invention, the pre-treating step comprises:
s11, washing the isosorbide reaction solution with isopropanol;
s12, separating;
and S13, performing rotary evaporation.
According to some embodiments of the invention, the separating in S12 is filtering.
The invention has the beneficial effects that:
the invention provides a method for separating and purifying isosorbide, which comprises the following steps: (1) the isopropanol is used for elution, during separation, the carbonization degree of the substrate subjected to reduced pressure distillation is not high, the carbonized product is dissolved in water and is easy to elute, the treatment and discharge of the eluent are simple, and the used high-boiling-point solvent can be recycled and accords with green chemistry; (2) during purification, the process is simple, the consumed time is short, and raw materials and solvents are not wasted to a great extent; (3) high yield and high product purity.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an HPLC chromatogram of a distillate in one embodiment of the present invention;
FIG. 2 is a simplified process flow diagram of one embodiment of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation. It is also to be understood that the reference to method steps and data associated therewith in this embodiment does not exclude the interposition of other combinations of method steps and proportions of data, and the endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and such ranges or values are to be understood as encompassing values close to these ranges or values and are to be considered as the scope of the practice of the invention.
For the description of the examples, the chemicals involved, if not specified, are commercially available from chemical companies. The product was detected by high performance liquid chromatography (LC1100) using Hi-Plex H as column, 1260RID as differential refractive index detector, water as mobile phase at 0.60mL/min and 60 deg.C as column.
Example 1
Preparing a reaction solution: adding 4g of solid acid catalyst (sulfonic acid resin) and 80g of sorbitol into a three-necked bottle, reacting for 5 hours at the reaction temperature of 140 ℃ and the pressure of 60mbar, dehydrating to prepare the isosorbide, washing out the reaction liquid by 160ml of isopropanol, filtering and separating the catalyst, and performing rotary evaporation to obtain 60g of reaction liquid to be separated, wherein the purity of the isosorbide is 73.00 percent by liquid chromatography detection.
Example 2
And (3) reduced pressure distillation: 15g of the reaction solution to be separated obtained in example 1 was taken, heated at 120 ℃ for 10min, the temperature was raised to 180 ℃ after the flow condition was good, and vacuum was applied under a pressure of 8 to 20Pa, after the product was distilled off, the reduced pressure distillation was completed after the temperature of a thermometer was lowered to 95 ℃, and the product was weighed to obtain 2.2g of a crude product (this is only the weight of the product obtained from the product receiving bottle, and the residue on the distillation elbow and the condenser tube was not taken into account, which is the same below).
Example 3
And (3) reduced pressure distillation: taking 15g of the reaction liquid to be separated obtained in the example 1, heating at 120 ℃ for 10min, after the flow condition is good, raising the temperature to 220 ℃, vacuumizing at the pressure of 8-20Pa, evaporating the product, reducing the temperature of a thermometer to 100 ℃, ending the reduced pressure distillation, weighing the product to obtain 8g of a crude product, and detecting the purity of the crude product to be 92% by liquid chromatography, wherein a spectrogram is shown in figure 1.
Example 4
And (3) reduced pressure distillation: 15g of the reaction solution to be separated obtained in example 1 was heated at 120 ℃ for 10min, after the flow condition was good, the temperature was raised to 260 ℃ and vacuum was applied, the pressure was 8-20Pa, after the product was distilled off, the temperature was lowered to 100 ℃ by a thermometer, the reduced pressure distillation was completed, and the product was weighed to obtain 7.6g of a crude product.
Example 5
And (3) reduced pressure distillation: taking 15g of the reaction liquid to be separated obtained in the example 1, adding 28g of polyethylene glycol 2000, heating at 120 ℃ for 10min, after the flow condition is good, raising the temperature to 220 ℃, vacuumizing, wherein the pressure is 8-20Pa, after the product is evaporated, reducing the temperature of a thermometer to 100 ℃, ending reduced pressure distillation, and weighing the product to obtain 9g of a crude product.
Example 6
And (3) recrystallization: 6g of the crude product obtained by the reduced pressure distillation in example 5 was taken and added into a three-necked flask, ethyl acetate was slowly added by a constant pressure dropping funnel, heating was carried out at 65 ℃ and 25ml of ethyl acetate, the solution was cooled to room temperature after being homogeneous, and was allowed to stand at 3 ℃ for 1 hour, and was allowed to stand at-10 ℃ for 1 hour, then taken out and filtered under reduced pressure, and was dried in a vacuum drying oven at 40 ℃ for 1 hour, and 5g of the crude product was weighed, and the purity was 98% by liquid chromatography.
Example 7
And (3) recrystallization: the crude product obtained in example 3 was distilled under reduced pressure to obtain a total of 6g, which was put in a three-necked flask, ethyl acetate was slowly added through a constant pressure dropping funnel, the mixture was heated at 30 ℃ and 100ml of ethyl acetate, and the solution was homogenized, cooled to room temperature, allowed to stand at 3 ℃ for 1 hour, allowed to stand at-10 ℃ for 1 hour, then taken out and filtered under reduced pressure, dried in a vacuum oven at 40 ℃ for 1 hour, and weighed to obtain 3g, and the purity thereof was 98% by liquid chromatography.
Example 8
And (3) filtering with activated carbon: the filtrate obtained in example 6 after filtration under reduced pressure was added with 20 wt.% of activated carbon, stirred and filtered, the filtrate was rotary evaporated, and the obtained product was weighed to obtain 0.3g, and the purity thereof was 96% by liquid chromatography.
While the embodiments of the present invention have been described in detail, it should be understood that the invention is not limited thereto, and that various simple modifications, including combinations of various materials of the same type and related parameters in any other suitable manner, can be made by those skilled in the art without departing from the present invention, and that such simple modifications and combinations should be considered as the present invention disclosed, and all fall within the scope of the present invention.
Claims (26)
1. A method for separating isosorbide comprising the steps of:
s1, mixing the isosorbide reaction liquid to be separated with high boiling point substances, and distilling to obtain a fraction, wherein the high boiling point substances are polyalcohol;
s2, dissolving the distillate by using a solvent, cooling and recrystallizing; carrying out primary filtration to obtain a first solid and a first filtrate;
s3, adding an adsorbent into the first filtrate, then carrying out secondary filtration to obtain a second filtrate, and separating the second filtrate to obtain a second solid;
wherein the isosorbide reaction liquid to be separated is the reaction liquid which is prepared by dehydrating sorbitol after the solid acid catalyst is recovered.
2. The method of claim 1, wherein the high boiling point substance is polypropylene glycol or polyethylene glycol.
3. The method of claim 1, wherein the high boiling point substance is polypropylene glycol 2000 or polyethylene glycol 2000.
4. The method according to claim 1, wherein the solvent is selected from one or more of ethyl acetate, isopropanol and ethanol.
5. The method of claim 1, wherein the adsorbent is selected from one or more of activated carbon, alumina, and silica gel.
6. The process according to any one of claims 1 to 5, wherein the distillation is a vacuum distillation.
7. The method according to any one of claims 1 to 5, wherein the first filtration is a reduced pressure filtration.
8. The method of any one of claims 1 to 5, wherein the separation is rotary evaporation in S3.
9. The method according to any one of claims 1 to 5, wherein the high boiling point substance added in the step of S1 is 50 to 300% w/w of the isosorbide reaction solution to be separated.
10. The method according to claim 9, wherein the high boiling point substance is added in an amount of 100 to 250% w/w based on the isosorbide reaction solution to be separated.
11. The method according to any one of claims 1 to 5, wherein the solvent in the step S2 is 100% to 1500% of the fraction in terms of v/w.
12. The method according to claim 11, wherein in the step of S2, the solvent is 150% to 500% of the fraction on a v/w basis.
13. The method according to any one of claims 1 to 5, wherein in the step S3, activated carbon is added in an amount of 5 to 200% by w/v based on the first filtrate.
14. The method as claimed in claim 13, wherein the activated carbon is added in an amount of 10-100% w/v of the first filtrate in the step of S3.
15. The method as claimed in any one of claims 1 to 5, wherein the mixing temperature in the step S1 is 100-300 ℃.
16. The method as claimed in claim 15, wherein the mixing temperature in the step of S1 is 150-280 ℃.
17. The method according to any one of claims 1 to 5, wherein the temperature of the distillation in the step S1 is 40 to 60 ℃ lower than the boiling point of the high boiling point substance.
18. The method according to any one of claims 1 to 5, wherein the temperature of the dissolution with the solvent in the S2 step is 25 to 70 ℃.
19. The method according to any one of claims 1 to 5, wherein in the step S2, the recrystallization condition is a standing time of 1 to 12 hours at-15 to 0 ℃.
20. The method according to any one of claims 1 to 5, wherein the recrystallization is carried out at 1 to 5 ℃ for 0.5 to 12 hours and then at-15 to-5 ℃ for 0.5 to 12 hours.
21. The method of any one of claims 1 to 5, wherein the recrystallization is repeated to equal to or greater than a specified purity.
22. The method of claim 21, wherein the purity is 96-99%.
23. The method according to any one of claims 1 to 5, further comprising a pretreatment step of washing the isosorbide reaction solution with a washing solution;
the washing liquid is one or more of isopropanol, ethyl acetate and propanol.
24. The method according to any one of claims 1 to 5, further comprising a pretreatment step of washing the isosorbide reaction solution with a washing liquid; the washing liquid is isopropanol.
25. The method of claim 23, wherein the preprocessing step comprises:
s11, washing the isosorbide reaction solution with isopropanol;
s12, separating;
and S13, performing rotary evaporation.
26. The method of claim 25, wherein the preprocessing step comprises:
s11, washing the isosorbide reaction solution with isopropanol;
s12, separating, namely filtering;
and S13, performing rotary evaporation.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1207257C (en) * | 2002-12-31 | 2005-06-22 | 曲阜师范大学 | Process for catalytically synthesizing isosorbierte by strong acid ion exchanging resin |
| CN101665497A (en) * | 2009-09-22 | 2010-03-10 | 南京工业大学 | Method for refining isosorbide by distillation and melt crystallization coupling technology |
| CN107722033A (en) * | 2017-11-06 | 2018-02-23 | 上海纳米技术及应用国家工程研究中心有限公司 | The method for adding hydrophobic ionic liquid to be evaporated under reduced pressure separation dehydration of sugar alcohols reaction product |
| CN109320522A (en) * | 2018-12-03 | 2019-02-12 | 山东天力药业有限公司 | A method of preparing isobide |
| CN109776557A (en) * | 2017-11-14 | 2019-05-21 | 鲁南制药集团股份有限公司 | A kind of preparation method of isobide |
-
2019
- 2019-09-29 CN CN201910934826.8A patent/CN112574228B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1207257C (en) * | 2002-12-31 | 2005-06-22 | 曲阜师范大学 | Process for catalytically synthesizing isosorbierte by strong acid ion exchanging resin |
| CN101665497A (en) * | 2009-09-22 | 2010-03-10 | 南京工业大学 | Method for refining isosorbide by distillation and melt crystallization coupling technology |
| CN107722033A (en) * | 2017-11-06 | 2018-02-23 | 上海纳米技术及应用国家工程研究中心有限公司 | The method for adding hydrophobic ionic liquid to be evaporated under reduced pressure separation dehydration of sugar alcohols reaction product |
| CN109776557A (en) * | 2017-11-14 | 2019-05-21 | 鲁南制药集团股份有限公司 | A kind of preparation method of isobide |
| CN109320522A (en) * | 2018-12-03 | 2019-02-12 | 山东天力药业有限公司 | A method of preparing isobide |
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