CN102731299B - 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
- CN102731299B CN102731299B CN201210223486.6A CN201210223486A CN102731299B CN 102731299 B CN102731299 B CN 102731299B CN 201210223486 A CN201210223486 A CN 201210223486A CN 102731299 B CN102731299 B CN 102731299B
- Authority
- CN
- China
- Prior art keywords
- extraction
- liquid
- methyl propionate
- water
- methanol
- 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.)
- Expired - Fee Related
Links
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 a kind of liquid-liquid extraction separation method of methyl propionate-Methanol-water azeotropic system.
Background technology
Methyl propionate is solvent and the sanitas of a kind of high-grade food, makeup; Be widely used as the anticorrosive additive of food, feed, to substitute Sodium Benzoate of current use etc., also can be used as that cellulose nitrate, nitro spray paint, the solvent of coating, varnish etc.Methyl propionate, as the basic raw material of organic synthesis industry, can pass through the senior nontoxic artificial reodorants such as ester-interchange method synthetic ethyl propionate, benzyl propionate, isoamyl propionate, propionic acid benzoic ether, for the production of alcoholic beverage industry and essence industry.At present, synthesizing mainly using the vitriol oil as catalyzer of methyl propionate, made by propionic acid and methyl alcohol direct reaction, in reaction after product, contain the free impurity such as acid, alcohol and water, methyl propionate easily with methyl alcohol, water formation binary azeotrope, therefore, adopt conventional distillation method to be difficult to obtain highly purified methyl propionate, and energy consumption is higher.In traditional industry, methyl propionate refining adopts sodium bicarbonate or saturated solution of sodium carbonate washing conventionally, then with rectifying after sodium carbonate or dried over sodium sulfate; Or with saturated sodium-chloride water solution washing, then with distilling under Vanadium Pentoxide in FLAKES exists after dried over anhydrous sodium carbonate, this process complexity, equipment is perishable, and alkali and salt cycle process energy consumption are high, and a large amount of " three wastes " discharge, easily forms series of environmental problems.Therefore, develop effective separating technology, be not only conducive to methyl propionate purity and improve, be more conducive to 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 one to overcome in traditional industry the methyl propionate product separation existing difficulty of purifying, effectively separate methyl propionate-Methanol-water azeotropic system, improve the liquid-liquid extraction separation method of methyl propionate-Methanol-water azeotropic system of methyl propionate purity.
Technical solution of the present invention is:
A kind of liquid-liquid extraction separation method of methyl propionate-Methanol-water azeotropic system, it is characterized in that: comprise the following steps: that double solvents using polynary alcohol and water is as extraction solvent, the mass ratio of raw material and extraction solvent is 1:0.5～5, methyl propionate-Methanol-water azeotropic system to methyl propionate and methanol aqueous solution carries out liquid-liquid extraction, after multi_layer extraction, raffinate is containing the methyl propionate of higher degree, extraction liquid is after underpressure distillation is processed, and the polyvalent alcohol that tower reactor is obtained and water are mixed in proportion and are mixed with fresh extraction solvent and recycle.
In the double solvents of polynary alcohol and water, the mass ratio of polynary alcohol and water is 1:0.1～1.
Described liquid-liquid extraction is multistage cross flow extraction process, when every one-level extracting operation, under normal temperature, raw material and extraction solvent is joined in extractor, stir 10～60 minutes, agitator shaft speed is 150～400 revs/min, and layering after static 30～60 minutes, carries out next stage processing.
Described liquid-liquid extraction is that raw material methyl propionate and methanol aqueous solution are sent in multi-stage counter current extraction tower, extraction agent polyvalent alcohol and extraction agent water are entered in multi-stage counter current extraction tower by side, He Ta middle and upper part, tower top respectively, at multi-stage counter current extraction tower Raw and two bursts of reverse contacts of the polynary alcohol and water of extraction agent that flow into multi-stage counter current extraction tower, continuous countercurrent extraction.
Described 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 conventionally, and its source is more extensive.
Extraction solvent of the present invention adopts the double solvents of polynary alcohol and water, here said " polyvalent alcohol ", i.e. gordian technique of the present invention: select a kind of solvent to be insoluble in methyl propionate, be soluble in first alcohol and water.From demixing phenomenon, halohydrocarbon, halogenated aryl hydrocarbon, ester class, ethers are soluble in methyl propionate and methyl alcohol, and slightly soluble or be insoluble in water does not possess above-mentioned condition; Organic acid, ethylene glycol, amine and sulfone class, all without demixing phenomenon, do not meet extraction conditions yet, and final discovery only has polyvalent alcohol to be demixing phenomenon.Because the viscosity of polyvalent alcohol is larger, the inconvenience that operates, further studies again the distribution condition of methyl propionate-Methanol-water azeotropic system in various polyvalent alcohols and water compounded solvents, and result shows 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 described polynary alcohol and water, the mass ratio of polynary alcohol and water is 1:0.1～1, preferably 1:0.5～1, optimum proportion is 1:0.5.
The present invention is taking the double solvents of polynary alcohol and water as extraction solvent, and raw material, after multistage cross flow extraction or multi-stage counter current extraction, can obtain the methyl propionate of purity more than 99.5%, and yield reaches 95%.Extraction liquid is after underpressure distillation is processed, and the polyvalent alcohol that tower reactor is obtained and water are mixed in proportion and 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 not to environment.
Brief description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 is multistage cross flow extraction process flow figure.
Fig. 2 is multi-stage counter current extraction process flow sheet.
Embodiment
Embodiment 1:
With reference to process flow sheet shown in Fig. 1, raw material is from methyl propionate-Methanol-water azeotropic system of propionic acid and methanol esterification reaction product-methyl propionate and methanol aqueous solution, and its composition transitivity data are as shown in table 1.Raw material is 20kg, and extraction agent S (weight ratio: glycerine: water=1:0.5) is 20kg.At ambient temperature, press technical process shown in Fig. 1, the extraction agent S that stock liquid (F) is sent into extractor and inflow fully stirs, stratification separates, extraction phase and extracting phase all reach equilibrium state in every grade of extractor, extraction liquid is after underpressure distillation is processed, and the glycerine that tower reactor is obtained and water are mixed in proportion and are mixed with fresh extraction agent S and can be recycled.Extraction phase E after separating
k(k=1,2,3) and extracting phase R
k(k=1,2,3) form (disregarding quantity of solvent) as shown in table 2, as shown in Table 2, after 3 cross current solvent extractions, can obtain the methyl propionate of purity more than 99.5%, and yield reaches 95%.The extracting and separating of the mixing solutions of the applicable methyl propionate of this technique and methyl alcohol, water arbitrary proportion, the mass ratio of raw material and extraction solvent is 1:1.
Table 1 raw material composition 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, stock liquid is from propionic acid and methanol esterification reaction product, and its composition transitivity data are as shown in table 1.Under normal temperature condition, stock liquid (F) to be sent in multi-stage counter current extraction tower, flow is 20kg/h; Extraction agent (weight ratio: glycerine: water=1:0.5) flow is 20kg/h, glycerine (S1) and water (S2) are entered in multi-stage counter current extraction tower by He Ta middle and upper part, tower top side line respectively, under being fully uniformly mixed, stock liquid (F) contacts with two strands of extraction agent G & W continuous countercurrents that flow into 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 4 stage countercurrent extractions, raffinate leaves standstill section (raffinate is more than 15 minutes this period of residence time) stratification through extracting phase, raffinate is containing the methyl propionate of purity more than 99.5%, other component concentration≤0.5%, the concrete composition of extraction phase and extracting phase and flow (disregarding quantity of solvent) as shown in table 3.At the bottom of extraction tower, extraction liquid is after underpressure distillation is processed, and the polyvalent alcohol that tower reactor is obtained and water are mixed in proportion and are mixed with fresh extraction solvent and recycle.
In Fig. 2,1, 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 described 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 described composite extractant S: water=1:0.1, S:F=5:1.All the other are with embodiment 1 or embodiment 2.
The inventive method is not subject to the restriction of above-mentioned concrete device and processing parameter, those skilled in the art are according to processing condition, can adjust or implement within the scope of the present invention corresponding conversion to relevant parameters, also can, according to the size of stock liquid treatment capacity, amplify accordingly in proportion.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 not to environment.
Claims (1)
1. the liquid-liquid extraction separation method of methyl propionate-Methanol-water azeotropic system, it is characterized in that: comprise the following steps: the methyl propionate-Methanol-water azeotropic system of raw material from propionic acid and methanol esterification reaction product-methyl propionate and methanol aqueous solution, its composition transitivity data are as shown in table 1; Raw material is 20kg, and extraction agent S is 20kg, weight ratio in extraction agent S: glycerine: water=1:0.5; At ambient temperature, the extraction agent S that stock liquid is sent into extractor and inflow fully stirs, stratification separates, extraction phase and extracting phase all reach equilibrium state in every grade of extractor, extraction liquid is after underpressure distillation is processed, and the glycerine that tower reactor is obtained and water are mixed in proportion and are mixed with fresh extraction agent S and can be recycled; After 3 cross current solvent extractions, obtain the methyl propionate of purity more than 99.5%; Extraction phase E after separating
k(k=1,2,3) and extracting phase R
k(k=1,2,3) form as table 2;
Table 1 raw material composition transitivity data
Table 2 multistage cross flow liquid-liquid extraction separating resulting
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 CN102731299A (en) | 2012-10-17 |
| CN102731299B true 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) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073423B (en) * | 2013-01-16 | 2014-04-23 | 南通大学 | Method for separating methyl propionate-methanol-water system by using rectification integration technology |
| CN103483192B (en) * | 2013-01-16 | 2015-06-17 | 南通大学 | High-yield separation method of methyl propionate-methanol-water system |
| 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 |
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 | 南京师范大学 | 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 | 南京师范大学 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102731299A (en) | 2012-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104496819B (en) | A kind of method that environment-friendly plasticizer is prepared in waste resource recycling | |
| CN105001087A (en) | Method and apparatus for producing formic esters by comprehensively utilizing metronidazole hydroxylation synthesis wastewater | |
| CN106397368A (en) | Fatty alcohol-polyoxyethylene ether glycidyl ether and preparation method thereof | |
| CN102731299B (en) | Liquid-liquid extraction separation method of methyl propionate-methanol-water azeotropic system | |
| CN102344220A (en) | Method for treating metronidazole waste water | |
| CN103827072A (en) | Method for recovering acetic acid | |
| CN102826956B (en) | Method for separating methyl propionate-methanol-water system by integration of salt-effect extraction and rectification | |
| CN102060831B (en) | Method for separating mixed tocopherols from plant oil deodorizer condensates | |
| CN101955427A (en) | Method for separating methyl acetate and methanol water solution through multistage cross flow liquid-liquid extraction | |
| CN104761452B (en) | A kind of purification process of butyl acrylate coarse product | |
| CN104874196B (en) | A kind of method processing sodium and ammonium acetate salt-diazonium Organic substance-methanol-water mixed solution | |
| CN103739520A (en) | Refining method of 3,4-dichlorobenzene isocyanate | |
| CN101863784A (en) | Methods for preparing and extracting betaine and betaine hydrochloride | |
| CN110981721A (en) | Method for continuously producing n-propyl acetate | |
| CN105001055B (en) | Based on mixed solvent as extractant isopropanol acetonitrile azeotropic mixture distillation and separation method | |
| CN102267898A (en) | Method for preparing diethyl succinate by using pyridine ionic liquid as catalyst | |
| CN102796029A (en) | Clean synthesis process for cosmetic grade 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid | |
| CN104892389B (en) | Technique for preparing oxalic acid by performing continuous reaction rectification hydrolysis on dimethyl oxalate | |
| CN105384629B (en) | A kind of energy-conserving and environment-protective production technology of the different monooctyl ester of lactic acid | |
| CN102627561B (en) | Preparation process for plasticizer-tributyl citrate | |
| CN101704727B (en) | Process for recovering tert butyl hydroquinone during production of butyl hydroxy anisol | |
| CN101434539B (en) | Preparation of benzyl acetate | |
| CN105061146A (en) | Batch distillation process for separating isopropanol-acetonitrile azeotrope through mixed extraction agent | |
| CN105001053A (en) | Isopropanol-propyl formate azeotrope rectification separation method based on mixed solvent as extracting agent | |
| CN107673970A (en) | A kind of preparation method of tributyrin |
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 |