CN103159586B - 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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- CN103159586B CN103159586B CN201310098177.5A CN201310098177A CN103159586B CN 103159586 B CN103159586 B CN 103159586B CN 201310098177 A CN201310098177 A CN 201310098177A CN 103159586 B CN103159586 B CN 103159586B
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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 dimethyl carbonate-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 synthesis, 1992 in Europe as the registration of non-toxic material, be called as green organic chemicals geared to the 21st century; In addition; because methylcarbonate has the excellent physical properties such as good intermiscibility, high-octane rating and specific inductivity; also the fields such as solvent, gasoline dope, lithium-ion battery electrolytes are widely used in, the products such as all right directly synthesised food additive, antioxidant, plant protection product, high-grade resin, fuel, pharmaceutical intermediate and tensio-active agent.The main method of current Synthesis of dimethyl carbonate is ester-interchange method and oxidative carbonylation of methanol method, the mixture (methylcarbonate massfraction 30%) of what these two kinds of methods obtained at first is all methylcarbonate and methyl alcohol, azeotropic temperature 64 DEG C, therefore be difficult to obtain highly purified methylcarbonate with conventional separation method, need to select special isolation technique to realize being separated.
Extracting rectifying is a kind of special extract rectification isolation technique, is applicable to the separation of azeotropic system.Extracting rectifying is by adding the relative volatility that extraction agent changes stock blend in rectifying tower, thus reaches the object 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 situation that treatment capacity is large.
Summary of the invention
The object of the invention is to propose a kind of dimethyl carbonate-methanol azeotropic mixture continuous extraction distillation and separation method, ethylene glycol is adopted to improve the relative volatility of dimethyl carbonate-methanol system as extraction agent, and ethylene glycol is the co-products 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:
Dimethyl carbonate-methanol azeotropic mixture continuous extraction distillation and separation method, it said method comprising the steps of:
(1) by dimethyl carbonate-methanol stock liquid, extraction agent ethylene glycol adds in storage tank respectively, then stock liquid is added tower reactor, is plugged thermometer, installs still liquid drawing mechanism;
(2) open tower top and the recirculated cooling water at the bottom of tower, opening power adjusts voltage, heats tower reactor, is heated to boiling, when tower top starts to reflux, regulates tower reactor heater voltage, keeps upflowing vapor amount, allows full tower keep total reflux 30 minutes;
(3) after tower top temperature is stable, start to add stock liquid and extraction agent, solvent ratio is 1 ~ 3, and opens reflux ratio controller and overhead extraction valve simultaneously;
(4) when the temperature-stable of tower top and tower reactor is constant, system reaches balance, starts sampling.
Described dimethyl carbonate-methanol azeotropic mixture continuous extraction distillation and separation method, the extraction agent of extracting rectifying described in it is ethylene glycol, is the co-products of transesterify Synthesis of dimethyl carbonate, and in extracting rectifying, glycol circulation uses.
Described dimethyl carbonate-methanol azeotropic mixture continuous extraction distillation and separation method, rectifying described in it adopts extractive distillation column, stage number is 30 pieces, feedstock plate is the 20th block of column plate, extractant feed plate is the 3rd block of column plate, establish heating kettle at the bottom of extractive distillation column tower, extracting rectifying column overhead connects condensing works and storage tank.
Advantage of the present invention is the relative volatility adopting ethylene glycol to improve dimethyl carbonate-methanol system as extraction agent, and ethylene glycol is the co-products of synthesis of dimethyl carbonate via transesterification, therefore originate more convenient, avoid and introduce the cost brought of other materials, easy to operate, be easy to control, achieve the recycle of solvent, energy expenditure reduces, and cost reduces, and separating effect is better, there is good economy, and be conducive to environmental protection.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of continuous extraction rectifying dimethyl carbonate-methanol azeotropic mixture;
Fig. 2 is for realizing extracting rectifying device schematic diagram of the present invention.
Embodiment
In figure: 1-ethylene glycol storage tank; 2-is containing alcohol waste tank; 3-spinner-type flowmeter; 4-thermometer; 5-tower reactor; 6-tower reactor discharging condenser; Thief hole at the bottom of 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; 13-overhead condenser.
The inventive method adopts and comprises extractive distillation column, extractive distillation column overhead condenser, and the device that heating kettle at the bottom of extractive distillation column tower and header tank and storage tank are formed carries out batch extracting rectified operation.Idiographic flow: first a part of stock liquid is added in tower reactor.The temperature controlling tower reactor is at ambient pressure 60 ~ 95 DEG C and carries out total reflux operation lasting 1 ~ 2 hour, then dimethyl carbonate-methanol mixture is entered in tower by the middle part of tower, extraction agent ethylene glycol adds in tower by high-order storage tank from close tower top, the mass flow rate of extraction agent is 1 ~ 3 times of mixture to be separated, reflux ratio is 2, after temperature-stable, 1 ~ 2 hour is the methanol product of more than 99% from overhead extraction massfraction, extraction methylcarbonate and extraction agent at the bottom of tower, tower bottom distillate enters extraction agent recovery tower, overhead extraction methylcarbonate, the extraction agent of extraction at the bottom of tower can recycle.
Embodiment one:
With flow path device shown in Fig. 2, extractive distillation column is 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 pieces, and tower top is condenser, tower reactor electricity consumption heating mantle heats, tower top discharging, trim the top of column electricity consumption magnet regula.This tower has 3 and 2 tower body thief holes at the rectifying section of extractive distillation column and stripping section, is convenient to detect liquid phase composition 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 piece of plate charging, and raw material is the 20th piece of plate charging, and solvent ratio is 1.5, and reflux ratio is 2.Be the methyl alcohol of 99.56% in the overhead extraction concentration of extractive distillation column, extraction methylcarbonate and extraction agent at the bottom of tower, tower bottom distillate enters 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 the ethylene glycol of extraction at the bottom of tower can recycle as extraction agent.
Embodiment two
With flow path device shown in Fig. 2, extractive distillation column is 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 pieces, and tower top is condenser, tower reactor electricity consumption heating mantle heats, tower top discharging, trim the top of column electricity consumption magnet regula.This tower has 3 and 2 tower body thief holes at the rectifying section of extractive distillation column and stripping section, is convenient to detect liquid phase composition 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 piece of plate charging, and raw material is the 20th piece of plate charging, and solvent ratio is 3, and reflux ratio is 2.Be the methyl alcohol of 99.75% in the overhead extraction concentration of extractive distillation column, extraction methylcarbonate and extraction agent at the bottom of tower, tower bottom distillate enters 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 the ethylene glycol of extraction at the bottom of tower can recycle as extraction agent.
Claims (2)
1. dimethyl carbonate-methanol azeotropic mixture continuous extraction distillation and separation method, is characterized in that, said method comprising the steps of:
(1) by dimethyl carbonate-methanol stock liquid, extraction agent ethylene glycol adds in storage tank respectively, then stock liquid is added tower reactor, is plugged thermometer, installs still liquid drawing mechanism;
(2) open tower top and the recirculated cooling water at the bottom of tower, opening power adjusts voltage, heats tower reactor, is heated to boiling, when tower top starts to reflux, regulates tower reactor heater voltage, keeps upflowing vapor amount, allows full tower keep total reflux 30 minutes;
(3) after tower top temperature is stable, start to add stock liquid and extraction agent, solvent ratio is 1 ~ 3, and opens reflux ratio controller and overhead extraction valve simultaneously;
(4) when the temperature-stable of tower top and tower reactor is constant, system reaches balance, starts sampling;
Described method is specially: first a part of stock liquid is added in tower reactor, the temperature controlling tower reactor is at ambient pressure 60 ~ 95 DEG C and carries out total reflux operation lasting 1 ~ 2 hour, then dimethyl carbonate-methanol mixture is entered in tower by the middle part of tower, extraction agent ethylene glycol adds in tower by high-order storage tank from close tower top, the mass flow rate of extraction agent is 1 ~ 3 times of mixture to be separated, reflux ratio is 2, after temperature-stable, 1 ~ 2 hour is the methanol product of more than 99% from overhead extraction massfraction, extraction methylcarbonate and extraction agent at the bottom of tower, tower bottom distillate enters extraction agent recovery tower, overhead extraction methylcarbonate, the extraction agent of extraction at the bottom of tower can recycle,
Described rectifying adopts extractive distillation column, and stage number is 30 pieces, and feedstock plate is the 20th block of column plate, and extractant feed plate is the 3rd block of column plate, establishes heating kettle at the bottom of extractive distillation column tower, and extracting rectifying column overhead connects condensing works and storage tank.
2. dimethyl carbonate-methanol azeotropic mixture continuous extraction distillation and separation method as claimed in claim 1, it is characterized in that, the extraction agent of described extracting rectifying is ethylene glycol, is the co-products of transesterify Synthesis of dimethyl carbonate, and in extracting rectifying, glycol circulation uses.
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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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| KR102611842B1 (en) | 2017-08-28 | 2023-12-07 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Method for separating dimethyl carbonate from methanol |
| 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 |
| CN113480430B (en) * | 2021-08-09 | 2022-05-27 | 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 |
| 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 |
| 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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| CN1528735A (en) * | 2003-10-16 | 2004-09-15 | 华东理工大学 | Method for joint production of dialkyl carbonate and diatomic alcohol |
| CN102060709A (en) * | 2009-11-14 | 2011-05-18 | 拜尔材料科学股份公司 | Method for purifying dialkyl carbonate |
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| JP2010168365A (en) * | 2008-12-26 | 2010-08-05 | Mitsubishi Chemicals Corp | Method for producing symmetric dialkyl carbonate and asymmetric dialkyl carbonate |
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| CN1212172A (en) * | 1997-09-24 | 1999-03-31 | 中国石油化工总公司 | Process for separating azeotrope of methanol and dimethyl carbonate |
| CN1528735A (en) * | 2003-10-16 | 2004-09-15 | 华东理工大学 | Method for joint production of dialkyl carbonate and diatomic alcohol |
| CN102060709A (en) * | 2009-11-14 | 2011-05-18 | 拜尔材料科学股份公司 | Method for purifying dialkyl carbonate |
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