CN114315764A - Method for refining and purifying tetrahydrofuran containing water - Google Patents
Method for refining and purifying tetrahydrofuran containing water Download PDFInfo
- Publication number
- CN114315764A CN114315764A CN202011030129.9A CN202011030129A CN114315764A CN 114315764 A CN114315764 A CN 114315764A CN 202011030129 A CN202011030129 A CN 202011030129A CN 114315764 A CN114315764 A CN 114315764A
- Authority
- CN
- China
- Prior art keywords
- tetrahydrofuran
- water
- reaction liquid
- conversion reaction
- distillation kettle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Furan Compounds (AREA)
Abstract
The invention discloses a method for refining and purifying tetrahydrofuran containing water, which comprises the following steps: s1, contacting the water-containing tetrahydrofuran with a strong acid cation exchange resin to obtain a first conversion reaction liquid; s2, contacting the first conversion reaction liquid obtained in the step S1 with strong-base cation exchange resin to obtain a second conversion reaction liquid; s3, distilling the second conversion reaction liquid in the step S2 to obtain crude tetrahydrofuran; s4, adding the crude tetrahydrofuran in the step S3 into a distillation kettle, adding a reducing agent to remove peroxide in the crude tetrahydrofuran, heating and distilling, and condensing and collecting low-moisture tetrahydrofuran evaporated in a storage tank; s5, pressing the low-moisture tetrahydrofuran in the storage tank into a distillation kettle by using nitrogen, adding a reagent which is dissolved in water and increases the boiling point of the water into the distillation kettle, heating the distillation kettle to evaporate the tetrahydrofuran, and collecting and condensing tetrahydrofuran vapor to obtain the purified tetrahydrofuran. The invention can reduce the water content of tetrahydrofuran to below 50 PPm.
Description
Technical Field
The invention relates to a purification method, in particular to a method for refining and purifying tetrahydrofuran containing water.
Background
Tetrahydrofuran is an important raw material for organic chemical industry and fine chemical industry, has good solubility for a plurality of organic and inorganic substances, can dissolve all compounds except polyethylene, polypropylene and fluororesin, is widely used as a reactive solvent, and is called as a universal solvent.
As methods for producing tetrahydrofuran, there are known several methods such as catalytic hydrogenation of furan, dehydration and cyclization of 1, 4-butanediol, and deesterification and cyclization of butane diacetate, and these methods are used to obtain tetrahydrofuran containing impurities such as aldehydes of dihydrofuran and water, so that tetrahydrofuran cannot be reused due to the impurities contained therein, is directly discarded, is wasted, pollutes the environment, and does not meet the development requirements of energy saving and emission reduction.
To this end, chinese patent application publication No. CN107746394A discloses a method for refining and purifying tetrahydrofuran containing water, which comprises the following steps: contacting aqueous tetrahydrofuran with a strong-acid cation exchange resin to convert dihydrofuran in the tetrahydrofuran into hydroxytetrahydrofuran to obtain a conversion reaction solution; distilling the step-converted reaction liquid to make an aqueous solution containing the hydroxyl tetrahydrofuran flow out from the bottom of the tower, and making the tetrahydrofuran and water be distilled out from the top of the tower together to obtain crude tetrahydrofuran; adding the crude tetrahydrofuran into a distillation kettle, adding a reducing agent to remove peroxide in the crude tetrahydrofuran, heating and distilling, and condensing and collecting the evaporated water-containing tetrahydrofuran in a storage tank; the water-containing tetrahydrofuran in the storage tank is pressed into a distillation kettle by nitrogen, a reagent which is dissolved in water and increases the boiling point of the water is added into the distillation kettle, then the distillation kettle is heated to 80-90 ℃ to evaporate the tetrahydrofuran, and the tetrahydrofuran vapor is collected and condensed to prepare the purified tetrahydrofuran. The tetrahydrofuran of the invention has high purity. However, the resulting tetrahydrofuran-water azeotrope still does not meet the low water requirement.
Disclosure of Invention
The invention aims to solve the technical problem that tetrahydrofuran contains impurities such as aldehyde of dihydrofuran, water and the like, and aims to provide a method for purifying water-containing tetrahydrofuran, which solves the problem that tetrahydrofuran cannot be reused due to the impurities.
The invention is realized by the following technical scheme:
the method for refining and purifying the water-containing tetrahydrofuran comprises the following steps:
s1, contacting the water-containing tetrahydrofuran with a strong acid cation exchange resin to convert dihydrofuran in the tetrahydrofuran into hydroxytetrahydrofuran to obtain a first conversion reaction liquid;
s2, contacting the first conversion reaction liquid obtained in the step S1 with strong-base cation exchange resin, and removing water in the first conversion reaction liquid to obtain a second conversion reaction liquid;
s3, distilling the second conversion reaction liquid in the step S2 to make the aqueous solution containing the hydroxyl tetrahydrofuran flow out from the bottom of the tower, and making the low-moisture tetrahydrofuran solution flow out from the top of the tower to obtain crude tetrahydrofuran;
s4, adding the crude tetrahydrofuran in the step S3 into a distillation kettle, adding a reducing agent to remove peroxide in the crude tetrahydrofuran, heating and distilling, and condensing and collecting low-moisture tetrahydrofuran evaporated in a storage tank;
s5, pressing the low-moisture tetrahydrofuran in the storage tank into a distillation kettle by using nitrogen, adding a reagent which is dissolved in water and increases the boiling point of the water into the distillation kettle, heating the distillation kettle to 80-90 ℃ to evaporate the tetrahydrofuran, and collecting and condensing tetrahydrofuran vapor to obtain the purified tetrahydrofuran.
Firstly, contacting water-containing tetrahydrofuran with a strong-acid cation exchange resin to remove dihydrofuran in the tetrahydrofuran, then contacting with a strong-base cation exchange resin to remove water in a first conversion reaction liquid to obtain a second conversion reaction liquid with low water content, and conveying the tetrahydrofuran by using nitrogen to play a role of nitrogen sealing; the invention increases the boiling point of water in tetrahydrofuran, heats the distilling kettle to 80-90 deg.C to distill out tetrahydrofuran, collects and condenses tetrahydrofuran vapor to obtain purified tetrahydrofuran, which can reduce the water content of tetrahydrofuran to below 50PPm and remove peroxide, antioxidant, mechanical impurity and other components in tetrahydrofuran.
In step S4, the crude tetrahydrofuran is adjusted to neutrality by adding an acid or a base before adding the reducing agent.
In step S4, the acid is sulfuric acid, and the base is sodium hydroxide or potassium hydroxide.
The heating temperature of the distillation still in step S5 was 85 ℃.
In step S5, the reagent is sodium chloride. Sodium chloride is dissolved in water to form brine, which has a boiling point higher than that of pure water.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the method for refining and purifying the water-containing tetrahydrofuran can reduce the water content of the tetrahydrofuran to below 50PPm, and can remove components such as peroxide, antioxidant, mechanical impurities and the like in the tetrahydrofuran;
2. the method for refining and purifying the water-containing tetrahydrofuran firstly contacts the water-containing tetrahydrofuran with strong acid cation exchange resin to remove dihydrofuran in the tetrahydrofuran; then, the reaction mixture is contacted with a strongly basic cation exchange resin to remove water in the first conversion reaction solution, thereby obtaining a second conversion reaction solution with low water content.
3. The refining and purifying method of the water-containing tetrahydrofuran uses nitrogen to convey tetrahydrofuran, and can play a role of nitrogen sealing.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
Example 1
The method for refining and purifying the water-containing tetrahydrofuran comprises the following steps:
s1, contacting the water-containing tetrahydrofuran with a strong acid cation exchange resin to convert dihydrofuran in the tetrahydrofuran into hydroxytetrahydrofuran to obtain a first conversion reaction liquid;
s2, contacting the first conversion reaction liquid obtained in the step S1 with strong-base cation exchange resin, and removing water in the first conversion reaction liquid to obtain a second conversion reaction liquid;
s3, distilling the second conversion reaction liquid in the step S2 to make the aqueous solution containing the hydroxyl tetrahydrofuran flow out from the bottom of the tower, and making the low-moisture tetrahydrofuran solution flow out from the top of the tower to obtain crude tetrahydrofuran;
s4, adding the crude tetrahydrofuran in the step S3 into a distillation kettle, adding a reducing agent to remove peroxide in the crude tetrahydrofuran, heating and distilling, and condensing and collecting the evaporated water-containing tetrahydrofuran in a storage tank;
s5, pressing the low-moisture tetrahydrofuran in the storage tank into a distillation kettle by using nitrogen, adding a reagent which is dissolved in water and increases the boiling point of the water into the distillation kettle, heating the distillation kettle to 80-90 ℃ to evaporate the tetrahydrofuran, and collecting and condensing tetrahydrofuran vapor to obtain the purified tetrahydrofuran. In step S3, the crude tetrahydrofuran is adjusted to neutrality by adding an acid or a base before adding the reducing agent. The acid is sulfuric acid, and the alkali is sodium hydroxide or potassium hydroxide. In step S4, the reagent is sodium chloride. Sodium chloride is dissolved in water to form brine, which has a boiling point higher than that of pure water.
Firstly, contacting water-containing tetrahydrofuran with a strong-acid cation exchange resin to remove dihydrofuran in the tetrahydrofuran, and then contacting with a strong-base cation exchange resin to remove water in the first conversion reaction liquid to obtain a second conversion reaction liquid with low water content. The tetrahydrofuran is conveyed by using nitrogen, so that the nitrogen sealing effect can be realized; the invention increases the boiling point of water in tetrahydrofuran, heats the distilling kettle to 80-90 deg.C to distill out tetrahydrofuran, collects and condenses tetrahydrofuran vapor to obtain purified tetrahydrofuran, which can reduce the water content of tetrahydrofuran to below 50PPm and remove peroxide, antioxidant, mechanical impurity and other components in tetrahydrofuran.
Example 2
The heating temperature of the distillation still in step S4 was 85 ℃ based on example 1. In this example, the purity of tetrahydrofuran was 98% or more, and the purity of dihydrofuran and aldehyde having 3 or less carbon atoms were 10ppm or less.
The above-mentioned strong-acid cation exchange resin and strong-base cation exchange resin can be selected as required by those skilled in the art.
Comparative example 1
The method for refining and purifying the water-containing tetrahydrofuran comprises the following steps:
s1, contacting the water-containing tetrahydrofuran with a strong acid cation exchange resin to convert dihydrofuran in the tetrahydrofuran into hydroxyl tetrahydrofuran to obtain a conversion reaction solution;
s2, distilling the conversion reaction liquid in the step S1 to make the aqueous solution containing the hydroxyl tetrahydrofuran flow out from the bottom of the tower, and making the tetrahydrofuran and water together distill from the top of the tower to obtain crude tetrahydrofuran;
s3, adding the crude tetrahydrofuran in the step S2 into a distillation kettle, adding a reducing agent to remove peroxide in the crude tetrahydrofuran, heating and distilling, and condensing and collecting the evaporated water-containing tetrahydrofuran in a storage tank;
s4, pressing the water-containing tetrahydrofuran in the storage tank into a distillation kettle by nitrogen, adding a reagent which is dissolved in water and increases the boiling point of the water into the distillation kettle, heating the distillation kettle to 80-90 ℃ to evaporate the tetrahydrofuran, collecting and condensing tetrahydrofuran vapor to obtain the purified tetrahydrofuran. In step S3, the crude tetrahydrofuran is adjusted to neutrality by adding an acid or a base before adding the reducing agent. The acid is sulfuric acid, and the alkali is sodium hydroxide or potassium hydroxide. In step S4, the reagent is sodium chloride. Sodium chloride is dissolved in water to form brine, which has a boiling point higher than that of pure water.
The water content of tetrahydrofuran is reduced to 100PPm, and simultaneously, the components such as peroxide, antioxidant, mechanical impurities and the like in the tetrahydrofuran can be removed.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. The method for refining and purifying the tetrahydrofuran containing water is characterized by comprising the following steps:
s1, contacting the water-containing tetrahydrofuran with a strong acid cation exchange resin to convert dihydrofuran in the tetrahydrofuran into hydroxytetrahydrofuran to obtain a first conversion reaction liquid;
s2, contacting the first conversion reaction liquid obtained in the step S1 with strong-base cation exchange resin, and removing water in the first conversion reaction liquid to obtain a second conversion reaction liquid;
s3, distilling the second conversion reaction liquid in the step S2 to make the aqueous solution containing the hydroxyl tetrahydrofuran flow out from the bottom of the tower, and making the low-moisture tetrahydrofuran solution flow out from the top of the tower to obtain crude tetrahydrofuran;
s4, adding the crude tetrahydrofuran in the step S3 into a distillation kettle, adding a reducing agent to remove peroxide in the crude tetrahydrofuran, heating and distilling, and condensing and collecting low-moisture tetrahydrofuran evaporated in a storage tank;
s5, pressing the low-moisture tetrahydrofuran in the storage tank into a distillation kettle by using nitrogen, adding a reagent which is dissolved in water and increases the boiling point of the water into the distillation kettle, heating the distillation kettle to 80-90 ℃ to evaporate the tetrahydrofuran, and collecting and condensing tetrahydrofuran vapor to obtain the purified tetrahydrofuran.
2. The method for purifying aqueous tetrahydrofuran according to claim 1 wherein in step S4, the crude tetrahydrofuran is neutralized by adding an acid or a base before adding the reducing agent.
3. The method for purifying tetrahydrofuran containing water as claimed in claim 1, wherein in step S4, the acid is sulfuric acid and the alkali is sodium hydroxide or potassium hydroxide.
4. The method for purifying aqueous tetrahydrofuran according to claim 1 wherein the heating temperature of the distillation still in step S5 is 85 ℃.
5. The method for purifying tetrahydrofuran containing water as claimed in claim 1, wherein the reagent in step S5 is sodium chloride; sodium chloride is dissolved in water to form brine, which has a boiling point higher than that of pure water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011030129.9A CN114315764A (en) | 2020-09-27 | 2020-09-27 | Method for refining and purifying tetrahydrofuran containing water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011030129.9A CN114315764A (en) | 2020-09-27 | 2020-09-27 | Method for refining and purifying tetrahydrofuran containing water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114315764A true CN114315764A (en) | 2022-04-12 |
Family
ID=81011490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011030129.9A Pending CN114315764A (en) | 2020-09-27 | 2020-09-27 | Method for refining and purifying tetrahydrofuran containing water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114315764A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002234883A (en) * | 2000-12-04 | 2002-08-23 | Mitsubishi Chemicals Corp | Method for purifying tetrahydrofuran |
| CN1386739A (en) * | 2002-06-21 | 2002-12-25 | 东营南开精细化工科技有限公司 | Process for dewatering and prifying tetrahydrofuran |
| CN1398860A (en) * | 2001-07-11 | 2003-02-26 | 三菱化学株式会社 | Tetrahydrofuran refining process |
| JP2003089694A (en) * | 2001-07-11 | 2003-03-28 | Mitsubishi Chemicals Corp | Method for purifying tetrahydrofuran |
| CN107746394A (en) * | 2017-12-06 | 2018-03-02 | 成都化润药业有限公司 | The polishing purification method of water-containing tetrahydrofuran |
-
2020
- 2020-09-27 CN CN202011030129.9A patent/CN114315764A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002234883A (en) * | 2000-12-04 | 2002-08-23 | Mitsubishi Chemicals Corp | Method for purifying tetrahydrofuran |
| CN1398860A (en) * | 2001-07-11 | 2003-02-26 | 三菱化学株式会社 | Tetrahydrofuran refining process |
| JP2003089694A (en) * | 2001-07-11 | 2003-03-28 | Mitsubishi Chemicals Corp | Method for purifying tetrahydrofuran |
| CN1386739A (en) * | 2002-06-21 | 2002-12-25 | 东营南开精细化工科技有限公司 | Process for dewatering and prifying tetrahydrofuran |
| CN107746394A (en) * | 2017-12-06 | 2018-03-02 | 成都化润药业有限公司 | The polishing purification method of water-containing tetrahydrofuran |
Non-Patent Citations (1)
| Title |
|---|
| 何领好等: "《现代药学实验技术（第一卷） 药学基本实验技术》", vol. 2016, 华中科技大学出版社, pages: 191 - 192 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101462977B (en) | Purification method of N,N-dimethylacetamide | |
| CN111574394B (en) | Method for treating carboxylic acid-containing DMF (dimethyl formamide) in sucralose production | |
| US20170327446A1 (en) | Method for Separation of Close-Boiling Mixture of Polyols | |
| KR20100051104A (en) | Process and apparatus for purification of industrial brine | |
| CN101570318A (en) | Method for producing electronic-stage hydrofluoric acid | |
| JP5511473B2 (en) | Purification method of ethylene glycol | |
| JP3244350B2 (en) | Method for producing high-purity acetic acid | |
| JP5101710B2 (en) | Purification method of ethylene glycol | |
| CN107746394A (en) | The polishing purification method of water-containing tetrahydrofuran | |
| JP4740432B2 (en) | Purification method of ethylene glycol | |
| CN114315764A (en) | Method for refining and purifying tetrahydrofuran containing water | |
| CN105461532A (en) | Clean production method for preparing acrolein and acrylic acid by propylene oxidation | |
| CN108863793B (en) | Preparation method of isopropyl acetate | |
| CN108329204B (en) | Concentration method of formic acid aqueous solution containing hydrogen chloride | |
| CN110902742A (en) | Method for recovering organic matters in high-concentration organic wastewater | |
| JP2001213825A (en) | High-purity 1,3-butylene glycol | |
| CN114181044B (en) | Preparation method of high-purity ditrimethylolpropane | |
| CN106698783B (en) | A kind for the treatment of process of epoxy grease plasticizer production waste water | |
| CN114249704B (en) | Preparation method of alkylene oxide | |
| CN111454210A (en) | Method for recycling formic acid solvent in production of 1, 3-dimethyl-2-imidazolidinone | |
| CN107108435A (en) | The method that formates is obtained from reactant mixture | |
| US10702792B2 (en) | Process for the isolation of levulinic acid | |
| CN109180614A (en) | The purifying technique of tetrahydrofuran in a kind of hexane, tetrahydrofuran and aqueous mixtures | |
| CN116283605A (en) | Method for preparing dimethylamine hydrochloride by using ODPA (organic chemical vapor deposition) production wastewater and application | |
| CN115181080B (en) | Separation process of methyl tertiary butyl ether-tetrahydrofuran-ethanol-water azeotropic system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |