CN102731299A - Liquid-liquid extraction separation method of methyl propionate-methanol-water azeotropic system - Google Patents
Liquid-liquid extraction separation method of methyl propionate-methanol-water azeotropic system Download PDFInfo
- Publication number
- CN102731299A CN102731299A CN2012102234866A CN201210223486A CN102731299A CN 102731299 A CN102731299 A CN 102731299A CN 2012102234866 A CN2012102234866 A CN 2012102234866A CN 201210223486 A CN201210223486 A CN 201210223486A CN 102731299 A CN102731299 A CN 102731299A
- Authority
- CN
- China
- Prior art keywords
- extraction
- liquid
- water
- methyl propionate
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a liquid-liquid extraction separation method of a methyl propionate-methanol-water azeotropic system. According to the invention, a composite solvent of polyhydric alcohol and water is adopted as an extraction solvent. A mass ratio of the raw material to the extraction solvent is 1:0.5-5. Liquid-liquid extraction is carried out upon the methyl propionate-methanol-water azeotropic system of methyl propionate and methanol aqueous solution. Layering and separation are carried out, and a raffinate contains high-concentration methyl propionate. The raffinate is subject to a vacuum distillation treatment. Polyhydric alcohol obtained at the tower cauldron is mixed with water according to a certain ratio, such that a fresh solvent is obtained for cyclic utilization. According to the invention, the composite solvent of polyhydric alcohol and water is adopted as the extraction solvent. The raw material is subjected to multi-stage cross-current extraction or multi-stage counter-current extraction, such that methyl propionate with purity above 99.5% can be obtained, and a yield reaches 95%.
Description
Technical field
The present invention relates to the liquid-liquid extraction separation method of a kind of methyl propionate-methyl alcohol-water azeotropic system.
Background technology
Methyl propionate is the solvent and the sanitas of a kind of high-grade food, makeup; Be widely used as the anticorrosive additive of food, feed, to substitute the Sodium Benzoate that uses at present etc., can be used as also that cellulose nitrate, nitro spray paint, the solvent of coating, varnish etc.Methyl propionate can pass through senior nontoxic artificial reodorants such as ester-interchange method synthetic ethyl propionate, benzyl propionate, isopentyl pyruvate, propionic acid benzoic ether as the basic raw material of organic synthesis industry, is used for the production of alcoholic beverage industry and essence industry.At present; Methyl propionate synthetic mainly with the vitriol oil as catalyzer, make by propionic acid and methyl alcohol direct reaction, react in the after product and contain impurity such as free acid, alcohol and water; Methyl propionate is prone to form binary azeotrope with methyl alcohol, water; Therefore, adopt the conventional distillation method to be difficult to obtain highly purified methyl propionate, and energy consumption is higher.The refining sodium hydrogencarbonate or the saturated solution of sodium carbonate of adopting usually of methyl propionate washed in the traditional industry, again with rectifying after yellow soda ash or the dried over sodium sulfate; Perhaps with the saturated sodium-chloride water solution washing, with distillation in the presence of Vanadium Pentoxide in FLAKES after the dried over anhydrous sodium carbonate, this process is complicated again, and equipment is perishable, and alkali and salt cycle process energy consumption are high, and a large amount of " three wastes " discharging is prone to form a series of environmental problems.Therefore, develop effective separating technology, not only help methyl propionate purity and improve, more help the Application and Development of energy-saving and emission-reduction and methyl propionate derived product.
Summary of the invention
The object of the present invention is to provide a kind of methyl propionate product separation existing difficulty of purifying that overcomes in the traditional industry; Effectively separate methyl propionate-methyl alcohol-water azeotropic system, improve the liquid-liquid extraction separation method of the methyl propionate-methyl alcohol-water azeotropic system of methyl propionate purity.
Technical solution of the present invention is:
The liquid-liquid extraction separation method of a kind of methyl propionate-methyl alcohol-water azeotropic system; It is characterized in that: comprise the following steps: that double solvents with polynary alcohol and water is as extraction solvent; The mass ratio of raw material and extraction solvent is 1:0.5～5; Methyl propionate-methyl alcohol-water azeotropic system to methyl propionate and methanol aqueous solution carries out liquid-liquid extraction, and after layering separated, raffinate contained the methyl propionate of higher degree; Extraction liquid is after underpressure distillation is handled, and polyvalent alcohol that the tower still is obtained and water proportional mixing are mixed with fresh extraction solvent and recycle.
The mass ratio of polynary alcohol and water is 1:0.1～1 in the double solvents of polynary alcohol and water.
Said liquid-liquid extraction is the multistage cross flow extraction process, during each grade extracting operation, under the normal temperature raw material and extraction solvent is joined in the extractor; Stirred 10～60 minutes; Agitator shaft speed is 150～400 rev/mins, and layering after static 30～60 minutes is carried out next stage and handled.
Said liquid-liquid extraction is that raw material methyl propionate and methanol aqueous solution are sent in the multi-stage counter current extraction tower; Extraction agent polyvalent alcohol and extraction agent water are got in the multi-stage counter current extraction tower by tower top and side, tower middle and upper part respectively; Raw material and two bursts of reverse contacts of the polynary alcohol and water of extraction agent that flow into the multi-stage counter current extraction tower, continuous countercurrent extraction in the multi-stage counter current extraction tower.
Said raw material methyl propionate and methanol aqueous solution can be the mixing solutionss of methyl propionate and methyl alcohol, water arbitrary proportion.Service water methyl propionate and methanol aqueous solution comprise 75%～90% methyl propionate, 10%～20% methyl alcohol and 0～15% water usually, and its source is more extensive.
Extraction solvent according to the invention adopts the double solvents of polynary alcohol and water, said here " polyvalent alcohol ", gordian technique promptly of the present invention: select a kind of solvent to be insoluble in methyl propionate, be soluble in the first alcohol and water.See that from demixing phenomenon halohydrocarbon, halogenated aryl hydrocarbon, ester class, ethers are soluble in methyl propionate and methyl alcohol, slightly soluble or be insoluble in water does not possess above-mentioned condition; Organic acid, terepthaloyl moietie, amine and sulfone class all do not have demixing phenomenon, do not meet extraction conditions yet, and final the discovery has only polyvalent alcohol to be demixing phenomenon.Because the viscosity of polyvalent alcohol is bigger, the distribution condition of methyl propionate-methyl alcohol-water azeotropic system in various polyvalent alcohols and water compounded solvents further studied in the inconvenience that operates again, and the result is illustrated in the separating effect the best in the double solvents of glycerine-water.Comprehensive each factor, selecting the double solvents of glycerine-water is best extraction solvent.
The double solvents of said polynary alcohol and water, the mass ratio of polynary alcohol and water are 1:0.1～1, preferred 1:0.5～1, and optimum proportion is 1:0.5.
The present invention is an extraction solvent with the double solvents of polynary alcohol and water, and raw material can obtain purity at the methyl propionate more than 99.5% behind multistage cross flow extraction or multi-stage counter current extraction, and yield reaches 95%.Extraction liquid is after underpressure distillation is handled, and polyvalent alcohol that the tower still is obtained and water proportional mixing are mixed with fresh extraction solvent and can be recycled.The methyl propionate product purity that separation method of the present invention obtains is high, and extraction process carries out at normal temperatures, and energy consumption is lower, and environment is not polluted.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is described further.
Fig. 1 is multistage cross flow extraction process flow figure.
Fig. 2 is the multi-stage counter current extraction process flow sheet.
Embodiment
Embodiment 1:
With reference to process flow sheet shown in Figure 1, raw material is from the methyl propionate-methyl alcohol-water azeotropic system of propionic acid and methanol esterification reaction product-methyl propionate and methanol aqueous solution, and it is as shown in table 1 that it forms the transitivity data.Raw material is 20kg, and (weight ratio: glycerine: water=1:0.5) is 20kg to extraction agent S.At ambient temperature; By technical process shown in Figure 1; The extraction agent S that liquid stock (F) is sent into extractor and inflow fully stirs, and standing demix separates, and extraction phase and extracting phase all reach equilibrium state in every grade of extractor; Extraction liquid is after underpressure distillation is handled, and glycerine that the tower still is obtained and water proportional mixing are mixed with fresh extraction agent S and can be recycled.Separate back extraction phase E
k(k=1,2,3) and extracting phase R
k(disregarding quantity of solvent) as shown in table 2 formed in (k=1,2,3), can be known that by table 2 behind 3 cross current solvent extractions, can obtain purity at the methyl propionate more than 99.5%, yield reaches 95%.The extracting and separating of the mixing solutions of suitable methyl propionate of this technology and methyl alcohol, water arbitrary proportion, the mass ratio of raw material and extraction solvent is 1:1.
Table 1 raw material is formed the transitivity data
Table 2 multistage cross flow liquid-liquid extraction separating resulting
Embodiment 2:
Adopt liquid-liquid extraction method as shown in Figure 2 to separate methyl propionate and methanol aqueous solution, liquid stock is from propionic acid and methanol esterification reaction product, and it is as shown in table 1 that it forms the transitivity data.Under normal temperature condition, liquid stock (F) to be sent in the multi-stage counter current extraction tower, flow is 20kg/h; (weight ratio: glycerine: water=1:0.5) flow is 20kg/h to extraction agent; Glycerine (S1) and water (S2) are got in the multi-stage counter current extraction tower by tower top and tower middle and upper part side line respectively; Fully mixing down; Liquid stock (F) contacts with two strands of extraction agent G & W continuous countercurrents that flow into the multi-stage counter current extraction tower, and extracting and separating is carried out in layering.Extraction phase and extracting phase all reach balance in every grade of extractor of multi-stage counter current extraction tower.After the extraction of 4 stage countercurrents; Raffinate is through the extracting phase section of leaving standstill (raffinate is more than 15 minutes in this section residence time) standing demix; Raffinate contains purity at the methyl propionate more than 99.5%; Other component concentration≤0.5%, extraction phase and extracting phase are concrete to be formed and flow (disregarding quantity of solvent) as shown in table 3.Extraction liquid is after underpressure distillation is handled at the bottom of the extraction tower, and polyvalent alcohol that the tower still is obtained and water proportional mixing are mixed with fresh extraction solvent and recycle.
Among Fig. 2,1, the extraction phase static segment; 2, liquid distributor; 3, extraction section; 4, extracting phase static segment.
Table 3 multi-stage counter current extraction separating resulting
Embodiment 3:
The composition glycerine of said composite extractant S: water=1:1, S:F=0.5:1.All the other are with embodiment 1 or embodiment 2.
Embodiment 4:
The composition glycerine of said composite extractant S: water=1:0.1, S:F=5:1.All the other are with embodiment 1 or embodiment 2.
The inventive method does not receive the restriction of above-mentioned concrete device and processing parameter; Those skilled in the art are according to processing condition; Can also can amplify accordingly in proportion within the scope of the present invention to there being related parameter to adjust or implement corresponding conversion according to the size of liquid stock treatment capacity.The methyl propionate product purity that separation method of the present invention obtains is high, and extraction process carries out at normal temperatures, and energy consumption is lower, and environment is not polluted.
Claims (5)
1. the liquid-liquid extraction separation method of methyl propionate-methyl alcohol-water azeotropic system; It is characterized in that: comprise the following steps: that double solvents with polynary alcohol and water is as extraction solvent; The mass ratio of raw material and extraction solvent is 1:0.5～5; Methyl propionate-methyl alcohol-water azeotropic system to methyl propionate and methanol aqueous solution carries out liquid-liquid extraction, and after layering separated, raffinate contained the methyl propionate of higher degree; Extraction liquid is after underpressure distillation is handled, and polyvalent alcohol that the tower still is obtained and water proportional mixing are mixed with fresh extraction solvent and recycle.
2. the liquid-liquid extraction separation method of methyl propionate-methyl alcohol according to claim 1-water azeotropic system is characterized in that: the mass ratio of polynary alcohol and water is 1:0.1～1 in the double solvents of polynary alcohol and water.
3. the liquid-liquid extraction separation method of methyl propionate-methyl alcohol according to claim 1 and 2-water azeotropic system; It is characterized in that: said liquid-liquid extraction is the multistage cross flow extraction process, during each grade extracting operation, under the normal temperature raw material and extraction solvent is joined in the extractor; Stirred 10～60 minutes; Agitator shaft speed is 150～400 rev/mins, and layering after static 30～60 minutes is carried out next stage and handled.
4. the liquid-liquid extraction separation method of methyl propionate-methyl alcohol according to claim 1 and 2-water azeotropic system; It is characterized in that: said liquid-liquid extraction is that raw material methyl propionate and methanol aqueous solution are sent in the multi-stage counter current extraction tower; Extraction agent polyvalent alcohol and extraction agent water are got in the multi-stage counter current extraction tower by tower top and side, tower middle and upper part respectively; Raw material and two bursts of reverse contacts of the polynary alcohol and water of extraction agent that flow into the multi-stage counter current extraction tower, continuous countercurrent extraction in the multi-stage counter current extraction tower.
5. the liquid-liquid extraction separation method of methyl propionate-methyl alcohol according to claim 1 and 2-water azeotropic system is characterized in that: said polyvalent alcohol is a glycerine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210223486.6A CN102731299B (en) | 2012-06-29 | 2012-06-29 | Liquid-liquid extraction separation method of methyl propionate-methanol-water azeotropic system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210223486.6A CN102731299B (en) | 2012-06-29 | 2012-06-29 | Liquid-liquid extraction separation method of methyl propionate-methanol-water azeotropic system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102731299A true CN102731299A (en) | 2012-10-17 |
| CN102731299B CN102731299B (en) | 2014-07-23 |
Family
ID=46987691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210223486.6A Expired - Fee Related CN102731299B (en) | 2012-06-29 | 2012-06-29 | Liquid-liquid extraction separation method of methyl propionate-methanol-water azeotropic system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102731299B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073423A (en) * | 2013-01-16 | 2013-05-01 | 南通大学 | Method for separating methyl propionate-methanol-water system by using rectification integration technology |
| CN103483192A (en) * | 2013-01-16 | 2014-01-01 | 南通大学 | High-yield separation method of methyl propionate-methanol-water system |
| CN112979462A (en) * | 2019-12-12 | 2021-06-18 | 中国石油天然气股份有限公司 | Method for improving conversion rate of fatty acid esterification reaction |
| CN118125403A (en) * | 2024-01-16 | 2024-06-04 | 中建安装集团有限公司 | Method for recycling polyol ether rectification residual liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1066584B (en) * | 1959-10-08 | Badische Anilin- ,&. Soda-Fabrik Aktiengesellschaft, Ludwigshafen/Rhein | Process for the separation of azeotropic mixtures of esters of aliphatic, saturated or unsaturated carboxylic acids and alcohols | |
| CN1526692A (en) * | 2003-09-22 | 2004-09-08 | ����ʦ����ѧ | Composite extracting and rectifying separation process of ethyl acetate |
| CN102120719A (en) * | 2010-08-26 | 2011-07-13 | 江苏沿江化工资源开发研究院有限公司 | Method for separating methyl acetate, methanol and water through two-trickle solvent side charging extractive distillation separating method and device thereof |
| CN102180791A (en) * | 2011-04-13 | 2011-09-14 | 天津大学 | Method for separating methyl acetate-methanol mixture by ionic liquid intermittent extractive rectification |
-
2012
- 2012-06-29 CN CN201210223486.6A patent/CN102731299B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1066584B (en) * | 1959-10-08 | Badische Anilin- ,&. Soda-Fabrik Aktiengesellschaft, Ludwigshafen/Rhein | Process for the separation of azeotropic mixtures of esters of aliphatic, saturated or unsaturated carboxylic acids and alcohols | |
| CN1526692A (en) * | 2003-09-22 | 2004-09-08 | ����ʦ����ѧ | Composite extracting and rectifying separation process of ethyl acetate |
| CN102120719A (en) * | 2010-08-26 | 2011-07-13 | 江苏沿江化工资源开发研究院有限公司 | Method for separating methyl acetate, methanol and water through two-trickle solvent side charging extractive distillation separating method and device thereof |
| CN102180791A (en) * | 2011-04-13 | 2011-09-14 | 天津大学 | Method for separating methyl acetate-methanol mixture by ionic liquid intermittent extractive rectification |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073423A (en) * | 2013-01-16 | 2013-05-01 | 南通大学 | Method for separating methyl propionate-methanol-water system by using rectification integration technology |
| CN103483192A (en) * | 2013-01-16 | 2014-01-01 | 南通大学 | High-yield separation method of methyl propionate-methanol-water system |
| CN103483192B (en) * | 2013-01-16 | 2015-06-17 | 南通大学 | High-yield separation method of methyl propionate-methanol-water system |
| CN112979462A (en) * | 2019-12-12 | 2021-06-18 | 中国石油天然气股份有限公司 | Method for improving conversion rate of fatty acid esterification reaction |
| CN112979462B (en) * | 2019-12-12 | 2023-01-10 | 中国石油天然气股份有限公司 | Method for improving conversion rate of fatty acid esterification reaction |
| CN118125403A (en) * | 2024-01-16 | 2024-06-04 | 中建安装集团有限公司 | Method for recycling polyol ether rectification residual liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102731299B (en) | 2014-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105001087A (en) | Method and apparatus for producing formic esters by comprehensively utilizing metronidazole hydroxylation synthesis wastewater | |
| CN102731299B (en) | Liquid-liquid extraction separation method of methyl propionate-methanol-water azeotropic system | |
| CN103772145B (en) | A kind of separation method of acetone hydrogenation preparing isopropanol | |
| CN106588599A (en) | Purification method of PODE (polyoxymethylene dimethyl ether) | |
| CN101362692A (en) | Technology method for producing isopropyl trifluoroacetate and apparatus | |
| CN104874196B (en) | A kind of method processing sodium and ammonium acetate salt-diazonium Organic substance-methanol-water mixed solution | |
| CN103272407B (en) | Method for removing residual formic acid in epoxidized fatty acid methyl esters or epoxidized soybean oil by use of eutectic solvent | |
| CN101139328B (en) | Novel process for synthesizing epoxy aliphatic acid methyl ester | |
| CN103508892A (en) | Synthetic method for phthalate compound | |
| CN102826956A (en) | Method for separating methyl propionate-methanol-water system by integration of salt-effect extraction and rectification | |
| CN101863784A (en) | Methods for preparing and extracting betaine and betaine hydrochloride | |
| CN101270141B (en) | Method for separating 24-dehydrogenation cholesterol and cholesterol | |
| CN101955427A (en) | Method for separating methyl acetate and methanol water solution through multistage cross flow liquid-liquid extraction | |
| CN101781172B (en) | Novel process for efficiently and continuously synthesizing 2-naphthol | |
| CN104447198B (en) | Separation technology for preparation of isopropanol by acetone hydrogenation | |
| CN104761452B (en) | A kind of purification process of butyl acrylate coarse product | |
| CN107311868A (en) | A kind of method for preparing p-tert-butyl benzoic acid methyl esters | |
| CN102795961B (en) | Device and method for synthesizing sec-butyl alcohol by continuous reaction-rectification | |
| CN102060831A (en) | Method for separating mixed tocopherols from plant oil deodorizer condensates | |
| CN102584740B (en) | Synthesis method for 4-methyl-5-(2-ethoxyl)-thiazole | |
| CN103772185B (en) | Device and method for removing moisture and heteroacids in acetic acid | |
| CN103772328B (en) | A kind of method reclaiming furfural from furfural stripped vapor phlegma | |
| CN101704727B (en) | Process for recovering tert butyl hydroquinone during production of butyl hydroxy anisol | |
| CN101503342A (en) | Method for separating diethoxymethane and ethanol by glycerol and water multi-stage countercurrent liquid-liquid extraction | |
| CN104262212A (en) | Method for continuously preparing 2,6-dinonyl naphthalene sulfonic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140723 Termination date: 20160629 |