CN111018719B - Method for purifying ethylenediamine - Google Patents
Method for purifying ethylenediamine Download PDFInfo
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- CN111018719B CN111018719B CN201911315324.3A CN201911315324A CN111018719B CN 111018719 B CN111018719 B CN 111018719B CN 201911315324 A CN201911315324 A CN 201911315324A CN 111018719 B CN111018719 B CN 111018719B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
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Abstract
The invention discloses a method for purifying ethylenediamine, which adopts C 2 ‑C 3 One or C of dihydric alcohol (B) 2 ‑C 3 The composite extractant consists of alcohol amine and sodium triiodide acetate or tert-butyl phenyl phosphate. Pumping the compound extractant and the crude ethylenediamine into an extraction tower by using an extractant feeding pump and a crude product feeding pump, and extracting the ethylenediamine from the top of the extraction tower; pumping the tower bottom material of the extraction tower into the rectification tower by using an extraction tower bottom pump, circulating the extractant in the rectification tower back to the extraction tower by using an extractant circulating pump, and extracting water from the top of the rectification tower. After the composite extractant is used, the tower height and the reflux ratio are reduced, the separation efficiency is improved, the extractant can be repeatedly used after being simply separated, the energy consumption is greatly reduced, and the production cost is reduced. Has the advantages of high separation efficiency, high purity of purified products, colorless and transparent products, good chromaticity and recyclable extracting agent.
Description
Technical Field
The invention belongs to the technical field of fine chemical separation and purification, and particularly relates to a method for purifying ethylenediamine.
Background
Ethylenediamine is a basic organic chemical raw material with wide application, and is mainly used for epoxy resin curing agents, pesticides, medicines, chelating agents and the like. In the production process of the technique for preparing the ethylenediamine by the reductive amination or the condensation amination of the ethanolamine, water is generated in the product. Since water (boiling point 100 ℃) and ethylenediamine (boiling point 117.15 ℃) are very close in boiling point, the two form the highest azeotrope, and conventional rectification is difficult to separate the two.
The crude product of ethylenediamine containing water obtained by industrial production of ethylenediamine is purified to obtain ethylenediamine, and the purification method generally adopts azeotropic distillation or extractive distillation to remove water. CN 10723837A discloses a method for purifying ethylenediamine, which comprises heating an extractant, feeding the heated extractant into an extraction tower from the upper part of the extraction tower, gasifying hydrous ethylenediamine, feeding the gasified hydrous ethylenediamine into the lower part of the extraction tower, reversely contacting the gasified hydrous ethylenediamine with the extractant from the upper part of the extraction tower in the extraction tower, discharging water from the top of the extraction tower, and separating a mixture of ethylenediamine and the extractant from the bottom of the extraction tower, wherein the extractant is diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether or diethylene glycol monobutyl ether; heating the mixture of the ethylenediamine and the extractant separated from the bottom of the extraction tower, then feeding the heated mixture into the middle part of a rectifying tower, rectifying the heated mixture in the rectifying tower, separating the ethylenediamine from the top of the rectifying tower, and discharging the extractant from the bottom of the rectifying tower. However, the implementation of the above invention has the following problems: (1) The ethylene diamine is heated in the tower kettle, so that the decomposition and yellowing phenomena exist, the decomposition products can be accumulated in the system, and the product chroma is more than 50 Hazen; (2) The purity of the ethylenediamine is low and can only reach 99.9 percent, and the requirement of electronic pure ethylenediamine can not be met; (3) The dosage of the extractant is large, and the proportion of the aqueous ethylenediamine to the extractant is 1:1 to 6. The above problems seriously hinder the industrialization of ethylenediamine.
Disclosure of Invention
In view of the defects or shortcomings in the prior art, the invention aims to provide a method for purifying ethylenediamine, which has the advantages of small using amount of an extracting agent, low energy consumption and high product quality.
The invention provides a method for purifying ethylenediamine, which comprises the following steps:
(1) Pumping the compound extractant and the crude ethylenediamine product into an extraction tower by using an extractant feeding pump and a crude ethylenediamine product feeding pump, wherein the number of theoretical plates of the extraction tower is not more than 15, and the feeding position of the crude ethylenediamine product is 10-13 theoretical plates; the feeding position of the extracting agent is 3-5 theoretical plates, the mass ratio of the crude ethylenediamine to the extracting agent is 1.5-0.8, the reflux ratio is 0.2-5, the ethylenediamine is extracted from the top of the extraction tower, the purity is more than 99.999%, and the water content is less than 10ppm;
(2) Pumping tower bottom materials of the extraction tower into a rectifying tower by using an extraction tower bottom pump, wherein the number of theoretical plates of the rectifying tower is not more than 10, the feeding position is 5-7 theoretical plates, the reflux ratio is 1-5, an extracting agent in the rectifying tower is circulated back to the extraction tower by an extracting agent circulating pump, and water is extracted from the top of the rectifying tower.
The main component of the composite extractant is C 2 -C 3 One or C of dihydric alcohol(s) 2 -C 3 The rest components of the alcohol amine are sodium triiodide acetate or tert-butyl phenyl diphenyl phosphate.
The sodium triiodide acetate in the composite extractant accounts for 0.5 percent of the total mass of the composite extractant.
The tert-butyl diphenyl phosphate in the composite extracting agent accounts for 0.3 percent of the total mass of the composite extracting agent.
The invention has the advantages of
According to the method for purifying the ethylenediamine, the tower height and the reflux ratio are reduced after the composite extracting agent is used, the separation efficiency is improved, the composite extracting agent can be recycled after simple separation, the energy consumption is greatly reduced, and the production cost is reduced; meanwhile, the ethylenediamine is directly extracted from the top of the tower, so that the product does not have the decomposition phenomenon caused by heating product flow in the tower kettle in the traditional process, the accumulation phenomenon of decomposition products in a system and the problem that the product chromaticity meets the requirement.
The method has the advantages of high separation efficiency, high purity of purified products, colorless and transparent products, product chromaticity less than 10 Hazen and recyclable extracting agent.
Drawings
FIG. 1 is a flow chart of the apparatus and process for purifying ethylenediamine according to the present invention.
The symbols in the figures represent:
b1, an extractant feeding pump, B2, a crude product feeding pump, B3 and an extraction tower; b4, a rectifying tower; b5, an extraction tower bottom pump, B6 and an extractant circulating pump
1 gets into extractant charge pump B1,2 get into crude charge pump B2,3 get into extraction tower B3 through extractant charge pump B1, 4 get into extraction tower B3 through crude charge pump B2, 5 flow out from extraction tower B3, 6 flow out from extraction tower B3 get into extraction tower cauldron bottom pump B5,7 flow out from extraction tower cauldron bottom pump B5 and get into rectifying column B4,8 flow out from rectifying column B4, 9 flow out from rectifying column B4 and get into extractant circulating pump B6,10 flow to extraction tower B3 from extractant circulating pump B6.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples.
As shown in FIG. 1, the method for purifying ethylenediamine, which is provided in the following example, employs equipment comprising an extractant feed pump B1, a crude product feed pump B2, an extraction column B3, a rectification column B4, an extraction column bottom pump B5 and an extractant circulation pump B6; an extractant feed pump B1 and a crude product feed pump B2 are connected with an extraction tower B3, ethylenediamine is extracted from the top of the extraction tower B3, the extraction tower B3 is connected with a rectifying tower B4 through an extraction tower kettle bottom pump B5, water is extracted from the top of the rectifying tower B4, and the rectifying tower B4 is connected with the extraction tower B3 through an extractant circulating pump B6.
The purity of the purified ethylenediamine is detected by gas chromatography, the chromatographic conditions are that a gasification chamber is 250 ℃, a detector is 250 ℃, a chromatographic column is a CAM column with the specification of 30m multiplied by 0.32mm multiplied by 0.25um, and the column temperature is 50 ℃.
The water content of the purified ethylenediamine was measured by the Karl Fischer method, and the chroma was measured by a CS-810 transmission spectrophotometer.
The following are examples given by the inventors, and the present invention is not limited to these examples.
Example 1:
respectively pumping an extracting agent and an ethylenediamine crude product into an extracting tower B3 by using an extracting agent feeding pump B1 and a crude product feeding pump B2, wherein the number of theoretical plates of the extracting tower B3 is 15, the feeding position of the ethylenediamine crude product is 10 theoretical plates, the main component of a composite extracting agent is ethylene glycol, the rest components are 0.5 percent of sodium triiodide acetate, the feeding position of the composite extracting agent is 3 theoretical plates, the mass ratio of the ethylenediamine crude product to the composite extracting agent is 1.5, the reflux ratio is 5, and the top of the extracting tower B3 is used for extracting ethylenediamine; the tower bottom material of the extraction tower B3 is pumped into a rectifying tower B4 by an extraction tower bottom pump B5, the number of theoretical plates of the rectifying tower B4 is 10, the feeding position is on the 5 th theoretical plate, the reflux ratio is 1, the tower top produced water of the rectifying tower B4, the extracting agent in the rectifying tower B4 is circulated back to the extraction tower B3 for reuse by an extracting agent circulating pump B6, the purity of the ethylenediamine is 99.99 percent by gas chromatography detection, the colorless transparent liquid (chroma is 9 Blacken), and the water content is 100ppm.
Example 2:
the same operation as in example 1, except that the number of theoretical plates of the extraction column B3 is 15, the feeding position of the crude ethylenediamine is 13 theoretical plates, the main component of the composite extractant is isopropanolamine, the remaining component is 0.3% of tert-butyl diphenyl phosphate, the feeding position of the extractant is 5 theoretical plates, the mass ratio of the crude ethylenediamine to the composite extractant is 1; the number of theoretical plates of the rectifying tower B4 is 10, the feeding position is on the 6 th theoretical plate, the reflux ratio is 1, the purity of the ethylenediamine is 99.999 percent through gas chromatography detection, colorless transparent liquid (chroma is 5 Blacken), and the water content is 8ppm.
Example 3:
the same operation as in example 1, except that the number of theoretical plates of the extraction column B3 is 15, the feeding position of the crude ethylenediamine product is 11 theoretical plates, the main component of the composite extractant is 1, 2-propanediol, the remaining component is 0.5% sodium triiodoacetate, the feeding position of the composite extractant is 4 theoretical plates, the mass ratio of the crude ethylenediamine product to the composite extractant is 1; the number of theoretical plates of the rectifying tower B4 is 10, the feeding position is on the 7 th theoretical plate, the reflux ratio is 1.
Example 4:
the same operation as in example 1, except that the number of theoretical plates of the extraction column B3 is 15, the feeding position of the crude ethylenediamine product is 12 theoretical plates, the main component of the composite extractant is ethanolamine, the remaining component is 0.5% sodium triiodoacetate, the feeding position of the composite extractant is 5 theoretical plates, the mass ratio of the crude ethylenediamine product to the composite extractant is 1; the number of theoretical plates of the rectifying tower B4 is 10, the feeding position is on the 6 th theoretical plate, the reflux ratio is 1.
Example 5:
the same operation as in example 1, except that the number of theoretical plates of the extraction column B3 is 15, the feeding position of the crude ethylenediamine product is 10 theoretical plates, the main component of the composite extractant is 1, 3-propanediol, the remaining component is 0.5% sodium triiodoacetate, the feeding position of the extractant is 3 theoretical plates, the mass ratio of the crude ethylenediamine product to the composite extractant is 1; the number of theoretical plates of the rectifying tower B4 is 10, the feeding position is on the 7 th theoretical plate, the reflux ratio is 1.
Comparative example 1:
the same operation as in example 1, except that the number of theoretical plates of the extraction column B3 is 15, the feeding position of the crude ethylenediamine is 10 theoretical plates, the extractant is ethanolamine, the feeding position of the extractant is 3 theoretical plates, the mass ratio of the crude ethylenediamine to the extractant is 1; the number of theoretical plates of a rectifying tower B4 is 10, the feeding position is on the 7 th theoretical plate, the reflux ratio is 1.
Comparative example 2:
the same operation as in example 1, except that the number of theoretical plates of the extraction column B3 is 15, the feeding position of the crude ethylenediamine product is 10 theoretical plates, the extractant is diethylene glycol monomethyl ether, the feeding position of the extractant is 3 theoretical plates, the mass ratio of the crude ethylenediamine product to the extractant is 1; the number of theoretical plates of a rectifying tower B4 is 10, the feeding position is on the 7 th theoretical plate, the reflux ratio is 1.
Claims (1)
1. A method for purifying ethylenediamine, comprising the steps of:
(1) By C 2 -C 3 One or C of dihydric alcohol(s) 2 -C 3 A composite extractant consisting of alcohol amine and sodium triiodide acetate accounting for 0.5 percent of the total mass of the composite extractant, or C 2 -C 3 One or C of dihydric alcohol(s) 2 -C 3 The composite extractant consists of alcohol amine and tertiary butyl diphenyl phosphate accounting for 0.3 percent of the total mass of the composite extractant, the composite extractant and the crude ethylenediamine are pumped into an extraction tower by an extractant feeding pump and a crude product feeding pump, the number of theoretical plates of the extraction tower is not more than 15, and the feeding position of the crude ethylenediamine is 10-13 theoretical plates; the feeding position of the extracting agent is 3-5 theoretical plates, the mass ratio of the crude ethylenediamine to the extracting agent is 1.5-0.8, the reflux ratio is 0.2-5, the ethylenediamine is extracted from the top of the extraction tower, the purity is more than 99.999%, and the water content is less than 10ppm;
(2) Pumping tower bottom materials of the extraction tower into a rectifying tower by using an extraction tower bottom pump, wherein the number of theoretical plates of the rectifying tower is not more than 10, the feeding position is 5-7 theoretical plates, the reflux ratio is 1-5, an extracting agent in the rectifying tower is circulated back to the extraction tower by an extracting agent circulating pump, and water is extracted from the top of the rectifying tower.
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| CN201911315324.3A CN111018719B (en) | 2019-12-19 | 2019-12-19 | Method for purifying ethylenediamine |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101723837A (en) * | 2009-12-10 | 2010-06-09 | 西安近代化学研究所 | Method for purifying ethylenediamine |
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| EP3700883B1 (en) * | 2017-10-27 | 2022-04-20 | Basf Se | Method for manufacturing ethylene amines |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101723837A (en) * | 2009-12-10 | 2010-06-09 | 西安近代化学研究所 | Method for purifying ethylenediamine |
Non-Patent Citations (2)
| Title |
|---|
| Comparison of alternative distillation processes for the maximum-boiling ethylenediamine dehydration system;Yu, Hao etal;《Chemical Engineering and Processing 》;20151231;84-105 * |
| 萃取精馏法分离乙二胺和H2O 的共沸物;王伟 等;《化学工程》;20141030;第42卷(第10期);摘要 * |
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