CN103159586A - Continuous extractive distillation separation method of dimethyl carbonate-methanol azeotropic mixture - Google Patents
Continuous extractive distillation separation method of dimethyl carbonate-methanol azeotropic mixture Download PDFInfo
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- CN103159586A CN103159586A CN2013100981775A CN201310098177A CN103159586A CN 103159586 A CN103159586 A CN 103159586A CN 2013100981775 A CN2013100981775 A CN 2013100981775A CN 201310098177 A CN201310098177 A CN 201310098177A CN 103159586 A CN103159586 A CN 103159586A
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Abstract
The invention discloses a continuous extractive distillation separation method of a dimethyl carbonate-methanol azeotropic mixture, and relates to a continuous extractive distillation method. The technical process of the method is as follows: ethylene glycol is used as an extraction agent at normal pressure; the solvent ratio is 1-3; the separated dimethyl carbonate-methanol azeotropic mixture is fed from the middle part of a tower, the extraction agent is fed from the top of the tower, and the reflux ratio is 2; high-purity methanol is extracted from the tower top of an extractive distillation tower, and the dimethyl carbonate and the extraction agent are extracted from the tower bottom; the fraction at the tower bottom enters an extraction agent recovery tower, and the reflux ratio is 3; and dimethyl carbonate is extracted from the tower top, and the extraction agent extracted from the tower bottom can be recycled. The method disclosed by the invention adopts ethylene glycol as an extraction agent, and improves the separation effect of the dimethyl carbonate-methanol azeotropic mixture; and since ethylene glycol is a co-production product in synthesizing dimethyl carbonate by a transesterification method, the source is conveniently available, and the cost caused by introducing other substances is avoided.
Description
Technical field
The present invention relates to a kind of continuous extraction rectificating method, particularly relate to a kind of methylcarbonate-methanol azeotropic mixture continuous extraction distillation and separation method.
Background technology
Methylcarbonate is a kind of basic organic chemistry raw material, is mainly used in the methylating of medication chemistry product, carbonylation reaction and synthetic, registers as non-toxicant in Europe in 1992, is called as green organic chemicals geared to the 21st century; In addition; because methylcarbonate has the good physical propertiess such as intermiscibility, high-octane rating and specific inductivity preferably; also be widely used in the fields such as solvent, gasoline dope, lithium-ion battery electrolytes, directly the products such as synthesised food additive, antioxidant, plant protection product, high-grade resin, fuel, pharmaceutical intermediate and tensio-active agent.The main method of Synthesis of dimethyl carbonate is ester-interchange method and oxidative carbonylation of methanol method at present, what these two kinds of methods obtained at first is all the mixture (methylcarbonate massfraction 30%) of methylcarbonate and methyl alcohol, 64 ℃ of azeotropic temperatures, therefore be difficult to obtain highly purified methylcarbonate with conventional separation method, need to select special isolation technique to realize separating.
Extracting rectifying is a kind of special extract rectification isolation technique, is applicable to the separation of azeotropic system.Extracting rectifying is by adding extraction agent to change the relative volatility of stock blend in rectifying tower, thereby reaches the purpose of separation.Extracting rectifying is divided into continuous extraction rectifying and batch extracting rectified by operating method.Batch extracting rectifiedly be suitable for the less situation for the treatment of capacity, and continuous extraction rectifying is also suitable for the large situation for the treatment of capacity.
Summary of the invention
The object of the invention is to propose a kind of methylcarbonate-methanol azeotropic mixture continuous extraction distillation and separation method, adopt ethylene glycol to improve the relative volatility of methylcarbonate-methanol system as extraction agent, and ethylene glycol is the coproduction product of synthesis of dimethyl carbonate via transesterification, the methylcarbonate product purity that the method is separated is high, simple to operate.
The present invention is realized by following technical proposals:
Methylcarbonate-methanol azeotropic mixture continuous extraction distillation and separation method, it said method comprising the steps of:
(1) with methylcarbonate-methanol feedstock liquid, extraction agent ethylene glycol adds respectively in storage tank, then stock liquid is added tower reactor, is plugged thermometer, and still liquid drawing mechanism is installed;
(2) open recirculated cooling water at the bottom of tower top and tower, opening power is transferred voltage, and tower reactor is heated, and is heated to boiling, when tower top begins to reflux, regulates the tower reactor heater voltage, keeps the rising quantity of steam, allows full tower keep total reflux 30 minutes;
(3) after tower top temperature is stable, begin to add stock liquid and extraction agent, solvent ratio is 1 ~ 3, and opens simultaneously reflux ratio controller and overhead extraction valve;
(4) when the temperature-stable of tower top and tower reactor was constant, system reached balance, began sampling, got final product.
Described methylcarbonate-methanol azeotropic mixture continuous extraction distillation and separation method, the extraction agent of its described extracting rectifying is ethylene glycol, is the coproduction product of transesterify Synthesis of dimethyl carbonate, in extracting rectifying, glycol circulation is used.
Described methylcarbonate-methanol azeotropic mixture continuous extraction distillation and separation method, extractive distillation column is adopted in its described rectifying, stage number is 30, the raw material feed plate is the 20th block of column plate, the extractant feed plate is the 3rd block of column plate, establish heating kettle at the bottom of the extractive distillation column tower, the extracting rectifying column overhead connects condensing works and storage tank.
Advantage of the present invention is to adopt ethylene glycol to improve the relative volatility of methylcarbonate-methanol system as extraction agent, and ethylene glycol is the coproduction product of synthesis of dimethyl carbonate via transesterification, therefore originate more convenient, avoided introducing the cost that other materials bring, easy to operate, be easy to control, realized the recycle of solvent, energy expenditure reduces, cost, and also separating effect is better, have good economy, and be conducive to environmental protection.
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Description of drawings
Fig. 1 is the process flow sheet of continuous extraction rectifying methylcarbonate-methanol azeotropic mixture;
Fig. 2 is for realizing extracting rectifying device schematic diagram of the present invention.
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Embodiment
In figure: 1-ethylene glycol storage tank; 2-contains pure waste tank; The 3-spinner-type flowmeter; The 4-thermometer; The 5-tower reactor; 6-tower reactor discharging condenser; Thief hole at the bottom of the 7-tower; 8-tower reactor overhead product tank; 9-overhead product storage tank; 10-electromagnetism reflux ratio controller; 11-tower top thief hole; 12-tower body thief hole; The 13-overhead condenser.
The inventive method adopts and comprises extractive distillation column, the extractive distillation column overhead condenser, and the device that at the bottom of the extractive distillation column tower, heating kettle and header tank and storage tank consist of carries out batch extracting rectified operation.Idiographic flow: first a part of stock liquid is added in tower reactor.the temperature of controlling tower reactor under normal pressure is 60 ~ 95 ℃ and carried out total reflux operation lasting 1 ~ 2 hour, then the middle part of methylcarbonate-carbinol mixture by tower entered in tower, extraction agent ethylene glycol is added in tower from close tower top by high-order storage tank, the mass flow rate of extraction agent is 1 ~ 3 times of mixture to be separated, reflux ratio is 2, until after temperature-stable 1 ~ 2 hour be methanol product more than 99% from the overhead extraction massfraction, extraction methylcarbonate and extraction agent at the bottom of tower, tower bottom distillate enters the extraction agent recovery tower, the overhead extraction methylcarbonate, at the bottom of tower, the extraction agent of extraction can recycle.
Embodiment one:
With flow path device shown in Figure 2, extractive distillation column is that internal diameter is 29mm, the stainless steel Dixon ring of in-built 3mm * 3mm, packed height is 1.5m, and number of theoretical plate is about 30, and tower top is condenser, tower reactor heats with electric heating cover, tower top discharging, trim the top of column electricity consumption magnet regula.This tower has 3 and 2 tower body thief holes at rectifying section and the stripping section of extractive distillation column, is convenient to detect liquid phase and forms massfraction.
Operate under normal temperature and pressure, separating dimethyl carbonate-methanol azeotropic mixture, wherein the mass content of methylcarbonate is 70%, and solvent ethylene glycol is the 3rd plate charging, and raw material is the 20th plate charging, and solvent ratio is 1.5, reflux ratio is 2.Be 99.56% methyl alcohol in the overhead extraction concentration of extractive distillation column, extraction methylcarbonate and extraction agent at the bottom of tower, tower bottom distillate enters the extraction agent recovery tower, stage number is 35, feed plate is the 17th block of column plate, reflux ratio is 3, and overhead extraction concentration is 99.86% methylcarbonate, and at the bottom of tower, the ethylene glycol of extraction can recycle as extraction agent.
Embodiment two
With flow path device shown in Figure 2, extractive distillation column is that internal diameter is 29mm, the stainless steel Dixon ring of in-built 3mm * 3mm, packed height is 1.5m, and number of theoretical plate is about 30, and tower top is condenser, tower reactor heats with electric heating cover, tower top discharging, trim the top of column electricity consumption magnet regula.This tower has 3 and 2 tower body thief holes at rectifying section and the stripping section of extractive distillation column, is convenient to detect liquid phase and forms massfraction.
Operate under normal temperature and pressure, separating dimethyl carbonate-methanol azeotropic mixture, wherein the mass content of methylcarbonate is 70%, and solvent ethylene glycol is the 3rd plate charging, and raw material is the 20th plate charging, and solvent ratio is 3, reflux ratio is 2.Be 99.75% methyl alcohol in the overhead extraction concentration of extractive distillation column, extraction methylcarbonate and extraction agent at the bottom of tower, tower bottom distillate enters the extraction agent recovery tower, stage number is 35, feed plate is the 17th block of column plate, reflux ratio is 3, and overhead extraction concentration is 99.89% methylcarbonate, and at the bottom of tower, the ethylene glycol of extraction can recycle as extraction agent.
Claims (3)
1. methylcarbonate-methanol azeotropic mixture continuous extraction distillation and separation method, is characterized in that, said method comprising the steps of:
(1) with methylcarbonate-methanol feedstock liquid, extraction agent ethylene glycol adds respectively in storage tank, then stock liquid is added tower reactor, is plugged thermometer, and still liquid drawing mechanism is installed;
(2) open recirculated cooling water at the bottom of tower top and tower, opening power is transferred voltage, and tower reactor is heated, and is heated to boiling, when tower top begins to reflux, regulates the tower reactor heater voltage, keeps the rising quantity of steam, allows full tower keep total reflux 30 minutes;
(3) after tower top temperature is stable, begin to add stock liquid and extraction agent, solvent ratio is 1 ~ 3, and opens simultaneously reflux ratio controller and overhead extraction valve;
(4) when the temperature-stable of tower top and tower reactor was constant, system reached balance, began sampling, got final product.
2. methylcarbonate as claimed in claim 1-methanol azeotropic mixture continuous extraction distillation and separation method, it is characterized in that, the extraction agent of described extracting rectifying is ethylene glycol, is the coproduction product of transesterify Synthesis of dimethyl carbonate, and in extracting rectifying, glycol circulation is used.
3. methylcarbonate as claimed in claim 1-methanol azeotropic mixture continuous extraction distillation and separation method, it is characterized in that, extractive distillation column is adopted in described rectifying, stage number is 30, the raw material feed plate is the 20th block of column plate, the extractant feed plate is the 3rd block of column plate, establishes heating kettle at the bottom of the extractive distillation column tower, and the extracting rectifying column overhead connects condensing works and storage tank.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439857A (en) * | 2015-12-09 | 2016-03-30 | 辽阳百事达化工有限公司 | Method and apparatus for producing methyl ethyl carbonate |
| CN105503524A (en) * | 2016-01-17 | 2016-04-20 | 济南大学 | Butanol-butyl formate azeotropic mixture extractive distillation method |
| CN106146310A (en) * | 2016-08-26 | 2016-11-23 | 中建安装工程有限公司 | A kind of device producing dimethyl carbonate and technique |
| CN106588655A (en) * | 2016-12-30 | 2017-04-26 | 开封中科新材料有限公司 | Device and production technology for synthesizing dimethyl carbonate through reaction between urea and methyl alcohol |
| DE102018214336A1 (en) | 2017-08-28 | 2019-02-28 | China Petroleum & Chemical Corporation | Process for the preparation of dimethyl carbonate from methanol |
| CN109422622A (en) * | 2017-08-28 | 2019-03-05 | 中国石油化工股份有限公司 | The method of extracting distillation separation C dimethyl phthalate and carbinol mixture |
| CN109422649A (en) * | 2017-08-28 | 2019-03-05 | 中国石油化工股份有限公司 | The purification process of dimethyl carbonate |
| CN109422650A (en) * | 2017-08-28 | 2019-03-05 | 中国石油化工股份有限公司 | The continuous separation method of dimethyl carbonate and carbinol mixture |
| CN109422647A (en) * | 2017-08-28 | 2019-03-05 | 中国石油化工股份有限公司 | The method of separating dimethyl carbonate and methanol azeotrope |
| CN109422648A (en) * | 2017-08-28 | 2019-03-05 | 中国石油化工股份有限公司 | Dimethyl carbonate and methanol azeotrope continuous extraction distillation and separation method |
| CN111377800A (en) * | 2020-03-16 | 2020-07-07 | 中国科学院过程工程研究所 | Separation device and separation method for coal-to-ethanol liquid-phase product |
| CN111848400A (en) * | 2020-08-26 | 2020-10-30 | 中建安装集团有限公司 | Device and process for preparing dimethyl carbonate by reactive distillation coupled extraction distillation |
| CN113480430A (en) * | 2021-08-09 | 2021-10-08 | 中国科学院山西煤炭化学研究所 | Device and method for producing high-purity dimethyl carbonate by catalytic extraction rectification |
| CN114230465A (en) * | 2021-12-13 | 2022-03-25 | 郑州中科新兴产业技术研究院 | Process for separating dimethyl carbonate and methanol azeotropic mixture |
| CN114621056A (en) * | 2022-04-19 | 2022-06-14 | 烟台国邦化工机械科技有限公司 | Process for separating dimethyl carbonate and methanol azeotrope |
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Cited By (27)
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| CN105439857A (en) * | 2015-12-09 | 2016-03-30 | 辽阳百事达化工有限公司 | Method and apparatus for producing methyl ethyl carbonate |
| CN105503524A (en) * | 2016-01-17 | 2016-04-20 | 济南大学 | Butanol-butyl formate azeotropic mixture extractive distillation method |
| CN105503524B (en) * | 2016-01-17 | 2017-12-12 | 济南大学 | A kind of butanol butyl formate azeotropic mixture extraction rectifying method |
| CN106146310A (en) * | 2016-08-26 | 2016-11-23 | 中建安装工程有限公司 | A kind of device producing dimethyl carbonate and technique |
| CN106588655A (en) * | 2016-12-30 | 2017-04-26 | 开封中科新材料有限公司 | Device and production technology for synthesizing dimethyl carbonate through reaction between urea and methyl alcohol |
| CN106588655B (en) * | 2016-12-30 | 2023-08-08 | 开封中科新材料有限公司 | Device and production process for synthesizing dimethyl carbonate by using reaction of urea and methanol |
| CN109422650B (en) * | 2017-08-28 | 2021-08-03 | 中国石油化工股份有限公司 | Continuous separation method of dimethyl carbonate and methanol mixture |
| CN109422622B (en) * | 2017-08-28 | 2021-11-30 | 中国石油化工股份有限公司 | Method for separating dimethyl carbonate and methanol mixture by extractive distillation |
| CN109422649A (en) * | 2017-08-28 | 2019-03-05 | 中国石油化工股份有限公司 | The purification process of dimethyl carbonate |
| CN109422650A (en) * | 2017-08-28 | 2019-03-05 | 中国石油化工股份有限公司 | The continuous separation method of dimethyl carbonate and carbinol mixture |
| CN109422647A (en) * | 2017-08-28 | 2019-03-05 | 中国石油化工股份有限公司 | The method of separating dimethyl carbonate and methanol azeotrope |
| CN109422648A (en) * | 2017-08-28 | 2019-03-05 | 中国石油化工股份有限公司 | Dimethyl carbonate and methanol azeotrope continuous extraction distillation and separation method |
| CN109422622A (en) * | 2017-08-28 | 2019-03-05 | 中国石油化工股份有限公司 | The method of extracting distillation separation C dimethyl phthalate and carbinol mixture |
| US10815185B2 (en) | 2017-08-28 | 2020-10-27 | China Petroleum & Chemical Corporation | Method for separating dimethyl carbonate from methanol |
| DE102018214336A1 (en) | 2017-08-28 | 2019-02-28 | China Petroleum & Chemical Corporation | Process for the preparation of dimethyl carbonate from methanol |
| CN109422648B (en) * | 2017-08-28 | 2021-05-11 | 中国石油化工股份有限公司 | Continuous extractive distillation separation method of dimethyl carbonate and methanol azeotrope |
| CN109422647B (en) * | 2017-08-28 | 2021-05-28 | 中国石油化工股份有限公司 | Process for separating dimethyl carbonate and methanol azeotrope |
| CN109422649B (en) * | 2017-08-28 | 2021-06-22 | 中国石油化工股份有限公司 | Method for purifying dimethyl carbonate |
| ES2702429A1 (en) * | 2017-08-28 | 2019-02-28 | China Petroleum & Chem Corp | Method for separating dimethyl carbonate from methanol (Machine-translation by Google Translate, not legally binding) |
| CN111377800A (en) * | 2020-03-16 | 2020-07-07 | 中国科学院过程工程研究所 | Separation device and separation method for coal-to-ethanol liquid-phase product |
| CN111377800B (en) * | 2020-03-16 | 2024-03-29 | 中国科学院过程工程研究所 | Separation device and separation method for coal-to-ethanol liquid phase product |
| CN111848400A (en) * | 2020-08-26 | 2020-10-30 | 中建安装集团有限公司 | Device and process for preparing dimethyl carbonate by reactive distillation coupled extraction distillation |
| CN113480430A (en) * | 2021-08-09 | 2021-10-08 | 中国科学院山西煤炭化学研究所 | Device and method for producing high-purity dimethyl carbonate by catalytic extraction rectification |
| CN114230465A (en) * | 2021-12-13 | 2022-03-25 | 郑州中科新兴产业技术研究院 | Process for separating dimethyl carbonate and methanol azeotropic mixture |
| CN114230465B (en) * | 2021-12-13 | 2024-01-26 | 郑州中科新兴产业技术研究院 | Process for separating dimethyl carbonate and methanol azeotropic mixture |
| CN114621056A (en) * | 2022-04-19 | 2022-06-14 | 烟台国邦化工机械科技有限公司 | Process for separating dimethyl carbonate and methanol azeotrope |
| CN114621056B (en) * | 2022-04-19 | 2023-10-27 | 烟台国邦化工机械科技有限公司 | Process method for separating dimethyl carbonate and methanol azeotrope |
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