CN105037162A - Method for continuous extraction distillation separation of dimethyl carbonate-methanol azeotropic mixture - Google Patents
Method for continuous extraction distillation separation of dimethyl carbonate-methanol azeotropic mixture Download PDFInfo
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- CN105037162A CN105037162A CN201510318174.7A CN201510318174A CN105037162A CN 105037162 A CN105037162 A CN 105037162A CN 201510318174 A CN201510318174 A CN 201510318174A CN 105037162 A CN105037162 A CN 105037162A
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- methylcarbonate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- 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
Abstract
The invention discloses a method for continuous extraction distillation separation of a dimethyl carbonate-methanol azeotropic mixture, and belongs to separation technologies of the dimethyl carbonate-methanol azeotropic mixture. According to the method, N,N-dimethylformamide, N-formylmorpholine or a mixture consisting of N,N-dimethylformamide and N-formylmorpholine in any proportion is used as an extracting agent. The operation condition of an extraction distillation tower and a solvent recovery tower are that the pressure is a normal pressure or reduced pressure, the ratio of a distillate at the top of the extraction distillation tower to the extracting agent is (0.5:1)-(10:1), and the feed (mass) ratio of the extracting agent to a mixture is (1:10)-(5:1). Two distillation towers are used in the method to achieve cycle utilization of the extracting agent. Methanol meeting requirements is obtained at the top of the extraction distillation tower, and the distillate at the bottom of the tower enters the solvent recovery tower; high-purity methyl carbonate is obtained at the top of the solvent recovery tower, and a high-purity extracting agent is obtained at the bottom of the tower; and a pump is used for pumping the extracting agent into the extraction distillation tower for cycle utilization. The method has the advantages that the extracting agent is adopted to destroy a dimethyl carbonate-methanol azeotropic system, and the aims of separating high-purity dimethyl carbonate and methanol and ensuring cycle utilization of the extracting agent are achieved. The continuous distillation has the advantages of high tower efficiency, high yield and the like.
Description
Technical field
The present invention relates to the continuous extraction distillation and separation method of a kind of methylcarbonate-methanol azeotropic mixture, belong to the isolation technique of methylcarbonate-methanol azeotropic mixture.
Background technology
Methylcarbonate (Dimethylcarbonate, be called for short DMC) be a kind of novel green Chemicals of chemical circles extensive concern both at home and abroad nearly ten years, owing to containing methyl, methoxyl group, carbonyl and carbomethoxy in its molecule, there is good chemical reactivity, the severe toxicity such as phosgene, methyl-sulfate, methyl chloride and methyl-chloroformate can be substituted or carcinogens carries out carbonylation, to methylate and the reaction such as transesterify generates multiple fine chemicals at numerous areas, therefore be described as " the new foundation stone " of 21 century organic synthesis.Its demand in the world also with annual 20% speed increase.And methyl alcohol is a kind of organic solvent, have important effect in synthesis, but can form azeotropic mixture due to methylcarbonate-methyl alcohol, the Separation Research therefore for this azeotropic system is necessary.
Feature according to present patent application retrieved related patent data, finds that the concentrating and separating device (application number: CN201020549621.2) of a kind of method (application number: CN200710121912.4) of separating dimethyl carbonate and methanol azeotrope, a kind of methylcarbonate and methyl alcohol and a kind of method (application number: CN200810145291.8) of separation of methanol and dimethyl carbonate azeotropic mixture have employed methyl alcohol and the methylcarbonate that mode that membrane separation technique and distillation operation be coupled carrys out separation and azeotropic respectively.But the operational condition that patent 200710121912.4 needs is harsh, especially working pressure comparatively large (0.1 ~ 0.6Mpa), can increase membrane separation unit cost of investment.And the mode of its direct saturation steam charging, also will increase the severity requirement to heat-insulating property between pipeline.Patent of invention 200710121912.4 and utility model patent CN201020549621.2 adopt inlet side condensation to collect the mode of permeate simultaneously, and also can increase the refrigeration power consumption of condensing equipment, energy consumption is larger.The patent such as the U.S., Japan is also studied for this azeotropic system, but and finds no great breakthrough.And this patent utilizes traditional extracting rectifying device and suitable extraction agent to be separated this azeotropic mixture, have simple to operate, column efficiency high.Relatively be applicable to the industrial large-scale plant that utilizes to produce.
Summary of the invention
The object of the present invention is to provide the continuous extraction distillation and separation method of a kind of methylcarbonate-methanol azeotropic mixture.High and the extraction agent of the purity of the isolated methylcarbonate of the method, methyl alcohol can recycle.
The present invention is achieved by the following technical solutions.Comprise the continuous extraction rectifier unit of extractive distillation column, solvent recovery tower, overhead condenser, tower bottom reboiler, pump and products pot composition, continuous extraction rectifying separation methylcarbonate-methanol azeotropic mixture.Its feature comprises following process:
With N, N-dimethylformamide (DMF), N-N-formyl morpholine N-or the two with arbitrary proportion composition mixture for extraction agent, extractive distillation column and solvent recovery tower operate under the following conditions, the extraction agent of extractive distillation column is entered and charge proportion is 0.5:1-10:1 at normal pressure or decompression, raw material enters from the bottom of extractive distillation column, extraction agent enters from the top of extractive distillation column, and the temperature of charging is 20-50 DEG C, and the temperature of extraction agent is 30-60 DEG C; When tower top temperature is 60-80 DEG C, overhead product is methyl alcohol, and reflux ratio is 3:1-10:1, and overhead product enters products pot V-0101, when column bottom temperature is 80-120 DEG C, methylcarbonate-extraction agent overhead product is entered solvent recovery tower, and feeding temperature is 20-60 DEG C, from the middle part charging of tower, when solvent recuperation column overhead temperatures is 85-95 DEG C, control reflux ratio is 3:1-10:1, by overhead extraction methylcarbonate, enters products pot V-0102; The extraction agent that at the bottom of tower, extraction purity is higher when the temperature at the bottom of tower is 140-160 DEG C, reboil ratio is 5:1-10:1, and the extraction agent pump distillated enters extractive distillation column and recycles.Thus can continuous extraction rectifying separation be carried out.
Idiographic flow (see photo): methylcarbonate-carbinol mixture is joined in heating kettle, open thermal source and the water of condensation of heating kettle, rectifying tower top to be extracted have backflow and tower top temperature stable after, extraction agent enters extractive distillation column from the top of tower, when the purity of overhead product reaches requirement, the methyl alcohol of overhead extraction enters products pot, methylcarbonate-the extraction agent distillated at the bottom of tower enters the middle part of solvent recovery tower, in the tower reactor of solvent recovery tower liquid level reach two/for the moment, open thermal source and the water of condensation of the heating kettle of solvent recovery tower.After the tower top temperature of solvent recovery tower is stable, the methylcarbonate product introduction products pot that tower top distillates, the extraction agent distillated at the bottom of tower and fresh extraction agent enter the top of extractive distillation column, and raw material constantly enters extractive distillation column always.Thus reach the optimal operational condition of continuous rectification separation.
The invention has the advantages that and use rationally effective extraction agent to destroy methylcarbonate-methanol azeotropic system, isolate highly purified methylcarbonate, methyl alcohol, adopt continuous extraction rectifying, good separating effect, productive rate is large.
Accompanying drawing explanation
Fig. 1 is apparatus of the present invention and schematic flow sheet.
T-0101 extractive distillation column T-0102 solvent recovery tower E-0101, E-0103 overhead condenser E-0102, E-0104 tower bottom reboiler V-0101, V-0102 products pot P-0101 pump.
Embodiment
Embodiment 1: adopt continuous rectification apparatus, drop in the heating kettle of extractive distillation column azeotropic mixture methylcarbonate-methyl alcohol 500L(wherein methyl alcohol be 80%, methylcarbonate is 20%, be mass percent), extraction agent selected by test is N, N-dimethylformamide, open the thermal source of extractive distillation column and the water of condensation of condenser, after rectifying tower tower top temperature-stable to be extracted, backflow for some time, extraction agent N is added on the top of extractive distillation column, N-dimethylformamide, the ratio of extraction agent and charging is 2:5, when the temperature of extractive distillation column is 60-80 DEG C, methanol product will be distillated in extracting rectifying column overhead, reflux ratio is 3:1.When the column bottom temperature of extractive distillation column is 80-120 DEG C, methylcarbonate-the extraction agent distillated at the bottom of tower is incorporated into the top of solvent recovery tower, reboil ratio is 1:5, and now in extractive distillation column, add raw material and extraction agent continuously, input speed is respectively 100L/h, 40L/h.Solvent recuperation column overhead have backflow and temperature remain on 90-100 DEG C substantially constant time, overhead extraction methylcarbonate.The reflux ratio of extraction is 2:1; When solvent recovery tower column bottom temperature is 140-160 DEG C, be driven into extractive distillation column by the extraction agent pump distillating purity at the bottom of tower higher, from the object reaching continuous rectification separation.
Embodiment 2: experimental installation and working method are with embodiment 1, and extraction agent adopts N-N-formyl morpholine N-.
Embodiment 3: experimental installation and working method are with embodiment 1, and extraction agent adopts the equal-volume mixture of N, N-dimethylformamide and N-N-formyl morpholine N-.
Claims (3)
1. the continuous extraction distillation and separation method of methylcarbonate-methanol azeotropic mixture, the method adopts the continuous extraction rectifier unit comprising extractive distillation column, solvent recovery tower, overhead condenser, tower bottom reboiler, pump and products pot composition, continuous extraction rectifying separation methylcarbonate-methanol azeotropic mixture.
2. the continuous extraction distillation and separation method of a kind of methylcarbonate-methanol azeotropic mixture as claimed in claim 1, it is characterized in that with N, N-dimethylformamide, N-N-formyl morpholine N-or the two with arbitrary proportion composition mixture for extraction agent.
3. the continuous extraction distillation and separation method of a kind of methylcarbonate-methanol azeotropic mixture as claimed in claim 2, it is characterized in that comprising following process: enter the extraction agent of extractive distillation column and charge proportion is 0.5:1-10:1 at normal pressure or decompression, raw material enters from the bottom of extractive distillation column, extraction agent enters from the top of extractive distillation column, the temperature of charging is 20-50 DEG C, and the temperature of extraction agent is 30-60 DEG C; When tower top temperature is 60-80 DEG C, overhead product is methyl alcohol, and reflux ratio is 3:1-10:1, overhead product enters products pot V-0101, when column bottom temperature is 80-120 DEG C, methylcarbonate-extraction agent overhead product is entered solvent recovery tower, feeding temperature is 20-60 DEG C; From the middle part charging of tower, when solvent recuperation column overhead temperatures is 85-95 DEG C, control reflux ratio is 3:1-10:1, by overhead extraction methylcarbonate, enters products pot V-0102; The extraction agent that at the bottom of tower, extraction purity is higher when the temperature at the bottom of tower is 140-160 DEG C, reboil ratio is 5:1-10:1, and the extraction agent pump distillated enters extractive distillation column and recycles, thus carries out continuous extraction rectifying separation.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510318174.7A CN105037162A (en) | 2015-06-11 | 2015-06-11 | Method for continuous extraction distillation separation of dimethyl carbonate-methanol azeotropic mixture |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107915642A (en) * | 2016-10-10 | 2018-04-17 | 中国石油化工股份有限公司 | The separation method of dimethyl carbonate and methanol |
| CN107915640A (en) * | 2016-10-10 | 2018-04-17 | 中国石油化工股份有限公司 | The extraction and rectification separation method of dimethyl carbonate and methanol |
| CN107915641A (en) * | 2016-10-10 | 2018-04-17 | 中国石油化工股份有限公司 | The method of extracting distillation separation C dimethyl phthalate and methanol |
| CN108218823A (en) * | 2018-01-09 | 2018-06-29 | 安徽卓润新型环保材料有限公司 | A kind of continuous treating method and device of high-purity 6-caprolactone |
| DE102018214336A1 (en) | 2017-08-28 | 2019-02-28 | China Petroleum & Chemical Corporation | Process for the preparation of dimethyl carbonate from methanol |
| 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 |
| 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 |
| 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 |
| CN112778087A (en) * | 2021-01-14 | 2021-05-11 | 山东科技大学 | Method for separating methanol-toluene azeotrope through continuous extractive distillation |
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| US4162200A (en) * | 1977-02-17 | 1979-07-24 | Basf Aktiengesellschaft | Preparation of pure dimethyl carbonate |
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| US4162200A (en) * | 1977-02-17 | 1979-07-24 | Basf Aktiengesellschaft | Preparation of pure dimethyl carbonate |
| CN1367772A (en) * | 1999-04-26 | 2002-09-04 | 通用电气公司 | Method of separating dimethyl carbonate and methanol |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107915642A (en) * | 2016-10-10 | 2018-04-17 | 中国石油化工股份有限公司 | The separation method of dimethyl carbonate and methanol |
| CN107915640A (en) * | 2016-10-10 | 2018-04-17 | 中国石油化工股份有限公司 | The extraction and rectification separation method of dimethyl carbonate and methanol |
| CN107915641A (en) * | 2016-10-10 | 2018-04-17 | 中国石油化工股份有限公司 | The method of extracting distillation separation C dimethyl phthalate and methanol |
| CN107915641B (en) * | 2016-10-10 | 2023-09-29 | 中国石油化工股份有限公司 | Method for separating dimethyl carbonate and methanol by extractive distillation |
| CN107915640B (en) * | 2016-10-10 | 2021-11-30 | 中国石油化工股份有限公司 | Extractive distillation separation method of dimethyl carbonate 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 |
| 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 |
| 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 |
| US10815185B2 (en) | 2017-08-28 | 2020-10-27 | China Petroleum & Chemical Corporation | Method for separating dimethyl carbonate from methanol |
| 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 |
| 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 |
| 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 |
| DE102018214336A1 (en) | 2017-08-28 | 2019-02-28 | China Petroleum & Chemical Corporation | Process for the preparation of dimethyl carbonate from methanol |
| CN108218823A (en) * | 2018-01-09 | 2018-06-29 | 安徽卓润新型环保材料有限公司 | A kind of continuous treating method and device of high-purity 6-caprolactone |
| CN112778087A (en) * | 2021-01-14 | 2021-05-11 | 山东科技大学 | Method for separating methanol-toluene azeotrope through continuous extractive distillation |
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