CN110590676B - Method for separating 1-octyl-3-methylimidazole lactate ionic liquid in benzene-methanol system - Google Patents
Method for separating 1-octyl-3-methylimidazole lactate ionic liquid in benzene-methanol system Download PDFInfo
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- CN110590676B CN110590676B CN201910825669.7A CN201910825669A CN110590676B CN 110590676 B CN110590676 B CN 110590676B CN 201910825669 A CN201910825669 A CN 201910825669A CN 110590676 B CN110590676 B CN 110590676B
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- C—CHEMISTRY; METALLURGY
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- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
- C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
- C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
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- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
- C07C29/84—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by extractive distillation
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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Abstract
The invention discloses a method for separating 1-octyl-3-methylimidazole lactate ionic liquid from a benzene-methanol system, and relates to a method for separating 1-octyl-3-methylimidazole lactate ionic liquid from a benzene-methanol system, which adopts a chemical oxidation method, takes hydrogen peroxide as an oxidant, lactic acid as an anion source and hydrogen bromide as a hydrogen source, and oxidizes bromide ions in an ionic liquid intermediate 1-octyl-3-methylimidazole bromide salt into bromine molecules in a water phase to remove the bromine molecules, so that the target ionic liquid 1-octyl-3-methylimidazole lactate is generated; the invention improves the traditional two-step synthesis method, and adopts a chemical oxidation method to prepare the 1-octyl-3-methylimidazole lactate ionic liquid. Compared with the traditional oxidation method, the method not only obviously shortens the reaction time, but also greatly improves the reaction yield; the synthesis speed of the ionic liquid containing weak acid radical is improved by adding a proper amount of hydrogen bromide source.
Description
Technical Field
The invention relates to a method for separating 1-octyl-3-methylimidazole lactate ionic liquid, in particular to a method for separating 1-octyl-3-methylimidazole lactate ionic liquid in a benzene-methanol system.
Background
Benzene and methanol are important organic raw materials, and can form an azeotrope system which is difficult to separate in the chemical production process, and the azeotrope is separated by a special rectification method such as reduced pressure rectification, azeotropic rectification, extractive rectification and the like according to specific situations. Extractive distillation as a common method of separating azeotropic mixtures from near-boiling mixtures, the determining factor is the choice of the extractant. As a novel extracting agent, the ionic liquid has attracted extensive attention due to the advantages of high separation efficiency, low volatility, good solubility and the like. At present, one of the main problems restricting the application of the ionic liquid extractant in extractive distillation is that the cost of the extractant is too high.
The tetramethylammonium methane sulfonate ([ N ] is synthesized by a chemical oxidation method in the earlier stage of a laboratory 1111 ]CH 3 SO 3 ) The results of 8 quaternary ammonium ionic liquids show that compared with the traditional method, the method greatly shortens the reaction time and improves the purity of the product. However, the method has the disadvantage that the method is only suitable for synthesizing ionic liquid with strong acid radicals such as methane sulfonic acid, nitric acid and the like as anions. For the ionic liquid with weak acid radical as anion such as lactate, the method has long synthesis time and low efficiency, and has no obvious advantages compared with the traditional method, thereby limiting the application of the method.
Disclosure of Invention
The invention aims to provide a method for separating 1-octyl-3-methylimidazole lactate ionic liquid for a benzene-methanol system, the 1-octyl-3-methylimidazole lactate ionic liquid is prepared by a chemical oxidation method, the reaction time is obviously shortened, and the reaction yield is greatly improved; the synthesis speed of the ionic liquid containing weak acid radical is improved by adding a proper amount of hydrogen bromide source.
The purpose of the invention is realized by the following technical scheme:
the method for separating the 1-octyl-3-methylimidazole lactate ionic liquid in the benzene-methanol system adopts a chemical oxidation method, hydrogen peroxide is used as an oxidant, lactic acid is used as an anion source, hydrogen bromide is used as a hydrogen source, and bromide ions in the ionic liquid intermediate 1-octyl-3-methylimidazole bromide salt are oxidized into bromine molecules in a water phase and removed, so that the target ionic liquid 1-octyl-3-methylimidazole lactate is generated;
the preparation method comprises the following preparation processes:
the method adopts a quantitative calculation method, considers from two aspects of separation efficiency and solubility, and selects 1-octyl-3-methylimidazole lactate ionic liquid as an effective separating agent for extracting, rectifying and separating a benzene-methanol azeotropic system through calculation and screening; synthesizing an intermediate 1-octyl-3-methylimidazole bromine salt ionic liquid through the first step in a two-step method, and then synthesizing a target ionic liquid 1-octyl-3-methylimidazole lactate through a chemical oxidation method instead of the second step ion exchange method in the traditional two-step method; in the oxidation method, hydrogen peroxide is used as an oxidant, lactic acid is used as an anion source, hydrogen bromide is used as a hydrogen source, and bromide ions in the ionic liquid intermediate 1-octyl-3-methylimidazole bromide salt are oxidized into bromine in a water phase to be removed, so that the target ionic liquid 1-octyl-3-methylimidazole lactate is generated.
According to the method for separating the 1-octyl-3-methylimidazole lactate ionic liquid in the benzene-methanol system, the synthesized 1-octyl-3-methylimidazole lactate ionic liquid is used as an extractant for the extraction, rectification and separation process of the benzene-methanol system; the added hydrogen peroxide is 2 to 4 times of the molar weight of bromide ions.
The method for separating the 1-octyl-3-methylimidazole lactate ionic liquid by using the benzene-methanol system comprises the steps of adding lactic acid and an ionic liquid intermediate 1-octyl-3-methylimidazole bromine according to a molar ratio of 1:1 is added.
According to the method for separating the 1-octyl-3-methylimidazole lactate ionic liquid in the benzene-methanol system, the added hydrogen bromide accounts for 5% -20% of the molar weight of the intermediate 1-octyl-3-methylimidazole bromine; and (3) extracting and removing bromine molecules generated in the reaction from the aqueous phase by taking carbon dichloride as a bromine removing agent.
The invention has the advantages and positive effects that:
the invention discloses a synthesis method of 1-octyl-3-methylimidazole lactate for extractive distillation of a benzene-methanol system, which improves the traditional two-step synthesis method, adopts a chemical oxidation method to prepare 1-octyl-3-methylimidazole lactate ionic liquid, and obviously shortens the reaction time and greatly improves the reaction yield compared with the traditional oxidation method; the synthesis speed of the ionic liquid containing weak acid radical is improved by adding a proper amount of hydrogen bromide source.
Detailed Description
The present invention will be described in detail with reference to examples.
The method firstly adopts a quantitative calculation method, and selects 1-octyl-3-methylimidazole lactate ionic liquid as an effective separating agent for separating a benzene-methanol azeotropic system by extractive distillation through a large amount of calculation and screening from the aspects of separation efficiency and solubility. Then according to the literature report, synthesizing an intermediate 1-octyl-3-methylimidazole bromine salt ionic liquid through the first step in a two-step method, and then synthesizing the target ionic liquid 1-octyl-3-methylimidazole lactate by adopting a chemical oxidation method to replace the second step ion exchange method in the traditional two-step method. In the oxidation method, hydrogen peroxide is used as an oxidant, lactic acid is used as an anion source, hydrogen bromide is used as a hydrogen source, and bromide ions in the ionic liquid intermediate 1-octyl-3-methylimidazole bromide salt are oxidized into bromine in a water phase to be removed, so that the target ionic liquid 1-octyl-3-methylimidazole lactate is generated. The selection of the hydrogen bromide source and the determination of the amount added are difficulties of the present invention. Hydrogen bromide is easier to ionize in water than lactic acid, so more hydrogen ions can be provided for the redox reaction of hydrogen peroxide, and the addition of hydrogen bromide can not cause other unexpected side effects due to the introduction of new ions in the product. The bromine ion impurities in the product are not easy to remove and the bromine removing agent is excessively consumed due to the excessive addition of the hydrogen bromide, and the reaction efficiency is reduced and the reaction time is prolonged due to the reduction of the reaction driving force due to the insufficient addition of the hydrogen bromide. The amount of addition thereof has to be determined by a large number of experiments.
Example 1: synthesizing an intermediate 1-octyl-3-methylimidazole bromide ionic liquid: 193g of 1-bromooctane was accurately weighed, charged into a three-necked flask equipped with a stirring rotor, and continuously charged with nitrogen gas to make an oxygen-free and anhydrous environment. 70g of azomethiazole is dripped into a dropping funnel, and after stabilization, the mixture is stirred for 1 hour in a constant temperature oil bath at 60 ℃, and the rotating speed of a stirring rotor is 15r/min. The obtained product is subjected to recrystallization in an aqueous solution to improve the purity, and the recrystallized product is dried in a vacuum drying oven at 70 ℃ for 24 hours to remove water. Synthesizing a target product 1-octyl-3-methylimidazole lactate ionic liquid by a chemical oxidation method: 90g of lactic acid, 17g of 47% aqueous hydrogen bromide and 5363 g of ionic liquid intermediate 1-octyl-3-methylimidazolium bromide 275.23g are added into a 1000ml three-neck bottle, 158g of 30% hydrogen peroxide is dropwise added under stirring, and the reaction is carried out for 1 hour. The bromine molecules generated during the reaction were washed with carbon dichloride in a separatory funnel. The water phase obtained is removed by rotary evaporation and then dried in a vacuum drying oven at 70 ℃ for 24h to obtain the product.
Example 2: synthesizing an intermediate 1-octyl-3-methylimidazole bromide ionic liquid: 193g of 1-bromooctane was accurately weighed, charged into a three-necked flask equipped with a stirring rotor, and continuously charged with nitrogen gas to make an oxygen-free and anhydrous environment. 80g of azomethiazole is dripped into a dropping funnel, and after stabilization, the mixture is stirred for 2 hours in a constant temperature oil bath at 60 ℃, and the rotating speed of a stirring rotor is 15r/min. The obtained product is subjected to recrystallization in an aqueous solution to improve the purity, and the recrystallized product is dried in a vacuum drying oven at 80 ℃ for 24 hours to remove water. Synthesizing a target product 1-octyl-3-methylimidazole lactate ionic liquid by a chemical oxidation method: 90g of lactic acid, 20g of 47% aqueous hydrogen bromide and 5363 g of ionic liquid intermediate 1-octyl-3-methylimidazole bromine 275.23 are taken and added into a 1000ml three-neck bottle, 180g of 30% hydrogen peroxide is added dropwise under stirring, and the reaction is carried out for 2 hours. The bromine molecules generated during the reaction were washed with carbon dichloride in a separatory funnel. The water phase obtained is removed by rotary evaporation and then dried in a vacuum oven at 70 ℃ for 24h to obtain the product.
Example 3: synthesizing an intermediate 1-octyl-3-methylimidazole bromide ionic liquid: 193g of 1-bromooctane was accurately weighed, charged into a three-necked flask equipped with a stirring rotor, and continuously charged with nitrogen gas to make an oxygen-free and anhydrous atmosphere. 90g of azomethiazole is dripped into a dropping funnel, and after stabilization, the mixture is stirred for 1.5 hours in a constant temperature oil bath at 60 ℃, and the rotating speed of a stirring rotor is 15r/min. The obtained product is subjected to recrystallization in an aqueous solution to improve the purity, and the recrystallized product is dried in a vacuum drying oven at 90 ℃ for 24 hours to remove water. Synthesizing a target product 1-octyl-3-methylimidazole lactate ionic liquid by a chemical oxidation method: adding 90g of lactic acid, 15g of 47% aqueous hydrogen bromide and 275.23g of ionic liquid intermediate 1-octyl-3-methylimidazolium bromide into a 1000ml three-neck bottle, dropwise adding 120g of 30% hydrogen peroxide while stirring, and reacting for 1 hour. The bromine molecules generated during the reaction were washed with carbon dichloride in a separatory funnel. The water phase was removed by rotary evaporation and then dried in a vacuum oven at 90 ℃ for 24h to give the product.
Claims (1)
1. The preparation method of the 1-octyl-3-methylimidazole lactate ionic liquid for separating the benzene-methanol system is characterized by adopting a chemical oxidation method, taking hydrogen peroxide as an oxidant, lactic acid as an anion source and hydrogen bromide as a hydrogen source, and oxidizing bromide ions in the ionic liquid intermediate 1-octyl-3-methylimidazole bromide salt into bromine molecules in a water phase to remove the bromine molecules so as to generate the target ionic liquid 1-octyl-3-methylimidazole lactate;
the preparation method comprises the following preparation processes:
the method adopts a quantitative calculation method, considers from two aspects of separation efficiency and solubility, and selects 1-octyl-3-methylimidazole lactate ionic liquid as an effective separating agent for extracting, rectifying and separating a benzene-methanol azeotropic system through calculation and screening; synthesizing an intermediate 1-octyl-3-methylimidazole bromine salt ionic liquid through the first step in a two-step method, and then synthesizing a target ionic liquid 1-octyl-3-methylimidazole lactate through a chemical oxidation method instead of the second step ion exchange method in the traditional two-step method; in the oxidation method, hydrogen peroxide is used as an oxidant, lactic acid is used as an anion source, hydrogen bromide is used as a hydrogen source, and bromide ions in the ionic liquid intermediate 1-octyl-3-methylimidazole bromide are oxidized into bromine simple substances in a water phase to be removed, so that the target ionic liquid 1-octyl-3-methylimidazole lactate is generated;
the synthesized 1-octyl-3-methylimidazole lactate ionic liquid is used as an extractant for the extraction, rectification and separation process of a benzene-methanol system; the added hydrogen peroxide is 2 to 4 times of the molar weight of bromide ions;
the added lactic acid and the ionic liquid intermediate 1-octyl-3-methylimidazole bromine are mixed according to a molar ratio of 1:1, adding;
the added hydrogen bromide accounts for 5-20% of the molar weight of the intermediate 1-octyl-3-methylimidazole bromine; and (3) extracting and removing bromine molecules generated by the reaction from the water phase by taking carbon dichloride as a bromine removing agent.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785524A (en) * | 2004-12-08 | 2006-06-14 | 北京化工大学 | Room temperature ionic liquid and its preparation method |
| CN102441312A (en) * | 2010-10-13 | 2012-05-09 | 北京化工大学 | Recyclable ionic liquid type carbon dioxide absorbent and preparation method thereof |
| CN105194982A (en) * | 2015-10-14 | 2015-12-30 | 黄锐 | Ionic liquid capable of absorbing sulfur dioxide as well as preparation method and application of ionic liquid |
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| US8071813B2 (en) * | 2007-05-03 | 2011-12-06 | Lawrence Livermore National Security, Llc | Methods of using ionic liquids having a fluoride anion as solvents |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785524A (en) * | 2004-12-08 | 2006-06-14 | 北京化工大学 | Room temperature ionic liquid and its preparation method |
| CN102441312A (en) * | 2010-10-13 | 2012-05-09 | 北京化工大学 | Recyclable ionic liquid type carbon dioxide absorbent and preparation method thereof |
| CN105194982A (en) * | 2015-10-14 | 2015-12-30 | 黄锐 | Ionic liquid capable of absorbing sulfur dioxide as well as preparation method and application of ionic liquid |
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| Title |
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| 化学氧化法制备季铵盐离子液体;李冬等;《沈阳化工大学学报》;20171231;210-213 * |
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