CN103772230B - The method of the mixing solutions of azeotropic extraction rectifying and liquid liquid layering integrated purification sodium salt, dimethyl formamide, toluene and water - Google Patents
The method of the mixing solutions of azeotropic extraction rectifying and liquid liquid layering integrated purification sodium salt, dimethyl formamide, toluene and water Download PDFInfo
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Abstract
A method for azeotropic extraction rectifying and liquid liquid layering integrated purification sodium salt, DMF, toluene and water mixed solution, adopts desalter to carry out preheating and desalination, by azeotropic distillation and extracting rectifying effective integration, in azeotropic extraction rectifying tower, realizes multicomponent separation.By the desalination of desalination evaporating pot after raw material preheating, add in azeotropic extraction rectifying tower with the modification extraction agent of tetramethylene sulfone and dioctyl phthalate (DOP) composition after desalination, control tower top, column bottom temperature carry out azeotropic extraction rectifying, tower top obtains toluene and water mixing gas, obtains the mixture of DMF and modification extraction agent at the bottom of tower; Toluene and water mixing gas, after condensation, are divided into content more than 99% toluene layer and toluene level lower than 0.08% water layer; The mixture of DMF and modification extraction agent is through solvent reclamation recycle column rectification process, and tower top obtains the DMF of more than 99.9%, obtains modification extraction agent, be circulated to azeotropic extraction rectifying tower at the bottom of solvent reclamation recycle column tower.
Description
Technical field
The present invention relates to the integrated technique that a kind of multicomponent mixture is separated, be specifically related to a kind of method of azeotropic extraction rectifying and liquid liquid layering integrated purification sodium salt-dimethyl formamide-toluene-water mixed solution.
Background technology
Dimethyl formamide (be called for short: DMF) and toluene be important industrial chemicals and solvent, be widely used in pharmacy and pesticide intermediate building-up process, in pharmacy and pesticide intermediate building-up process, adopt above-mentioned solvent, easily form the mixing solutions of sodium salt, DMF, toluene and water.Domestic and international recovery and treatment process for containing sodium salt, DMF and toluene in waste water at present mainly contains physico-chemical process, biochemical process and chemical hydrolysis.Adopt biochemical process and chemical hydrolysis all can destroy DMF and toluene structure.The biochemical process treatment time is long, degraded is not thorough, and in addition, DMF can make microorganism poisoning, causes extreme shock to biological treatment; Chemical method does not reach the object reclaiming DMF and toluene, easily causes secondary pollution.
To above-mentioned mixed solution as taked effective separation method, not only can reclaim DMF and toluene, reaching the object of process waste water simultaneously, reduce treating processes cost.Adopt low boiling point solvent as CH
2cl
2, chloroform, dichlorobenzene, benzene, pimelinketone or methyl-phenoxide etc. carry out liquid-liquid extraction as extraction agent, recyclable DMF, but need to be separated further containing the mixed solvent of extraction agent after extraction, reach 1 ~ 3% containing organic solvent in water after being separated, easily cause secondary pollution.For high density DMF and toluene (nearly 100g/L) waste water, distillation method is separated DMF, toluene and water, and the DMF of recovery and toluene can be back to production, but the waste water COD after being separated reaches 40000PPM, and process energy consumption is higher; If DMF and toluene mass concentration are lower than 50g/L in waste water, this method cost recovery will increase considerably, very uneconomical.Absorption method has the features such as technical process is short, simple to operate, recovering effect is good, but the mixing organism after absorption needs process further, and adsorbent reactivation needs high energy consumption.
Summary of the invention
The object of the present invention is to provide the technique of a kind of azeotropic extraction rectifying and liquid liquid layering integrated purification sodium salt, DMF, toluene and water mixed solution, compared with traditional technology, it is fairly simple that the present invention has processing step, through flash liberation, content, the yield of DMF and toluene are higher, and after being separated, the COD of water is lower than 800PPM; Extraction agent used is convenient to regeneration and recycle, and sepn process energy consumption is low.
For achieving the above object, the present invention adopts following technical scheme:
A method for azeotropic extraction rectifying and liquid liquid layering integrated purification sodium salt-DMF-toluene-water mixed solution, comprises the following steps:
1) after raw material sodium salt, DMF, toluene and water mixed solution preheating, again by the desalination of desalination evaporating pot, mixing solutions after desalination adds azeotropic extraction rectifying tower from the middle and lower part of azeotropic extraction rectifying tower, modification extraction agent adds in azeotropic extraction rectifying tower by the middle and upper part of azeotropic extraction rectifying tower, and described modification extraction solvent is the mixed solvent of tetramethylene sulfone and dioctyl phthalate (DOP); Control tower top, column bottom temperature, mixing solutions is at azeotropic extraction rectifying tower through azeotropic extraction rectifying, and tower top obtains toluene and water mixing gas, obtains the mixture of DMF and modification extraction agent at the bottom of tower;
2) toluene and water mixing gas are after condensation, are divided into toluene layer and water layer, and toluene layer is containing the toluene of more than 99% (mass content, following content is mass content), and water layer toluene level is lower than 0.08%; Toluene is partly refluxed to azeotropic extraction rectifying tower;
3) mixture of DMF and modification extraction agent is through solvent reclamation recycle column rectification process, and solvent reclamation recycle column tower top obtains the DMF of 99.9%, obtains modification extraction agent, be circulated to azeotropic extraction rectifying tower at the bottom of solvent reclamation recycle column tower.
The inventive method establishes a kind of azeotropic extraction rectificating method, by traditional azeotropic distillation and extracting rectifying effective integration in the same apparatus, same azeotropic extraction rectifying tower realizes DMF, toluene is separated with water, simplify the technological process of production.
In described method, the tower top of azeotropic extraction rectifying tower and the temperature at the bottom of tower are respectively 83.8 ~ 84.5 DEG C and 95.7 ~ 97.5 DEG C.
In described method, the mass ratio of raw material and modification extraction agent is 1:0.4 ~ 1.0.
In described method, described modification extraction solvent is the sulfolane solution containing 15 ~ 20% dioctyl phthalate (DOP)s.
In described method, mixing solutions and azeotropic extractive distillation column overhead vapours carry out heat exchange and carry out preheating.
Azeotropic extraction rectifying of the present invention and liquid liquid layering integrated purification sodium salt, DMF, the method of toluene and water mixed solution, concrete steps are as follows: sodium salt, DMF, toluene and water mixed solution are 1. through azeotropic extraction rectifying tower tower top steam preheating, again by after the desalination of desalination evaporating pot, add in azeotropic extraction rectifying tower by the middle and lower part of azeotropic extraction rectifying tower, azeotropic extraction rectifying tower tower top, column bottom temperature is respectively 83.8 ~ 84.5 DEG C and 95.7 ~ 97.5 DEG C, 6. modification extraction agent (adds 15-20wt% dioctyl phthalate (DOP)) in the upper position charging of azeotropic extraction rectifying tower in tetramethylene sulfone, after azeotropic distillation and extracting rectifying, 3. azeotropic extraction rectifying tower tower top is the mixing gas of toluene and water, after raw material condensation (with the 1. heat exchange of charging mixing solutions) and cryogenic condensation, DEG C (raw material condensation effectively utilizes the heat of azeotropic extraction rectifying tower tower top gas in fluid temperature≤20, cryogenic condensation ensures that tower top gas is condensed into liquid), be divided into toluene layer 4. with water layer 5., 4. toluene layer is more than 99.5% toluene, 5. water layer is the water (toluene is lower than 0.08%) of more than 99.9%, it is 8. the mixed solution of modification extraction agent and DMF at the bottom of azeotropic extraction rectifying tower, mixed solution is 8. through solvent reclamation recycle column rectification process, solvent reclamation circulation tower top distillates the DMF solution that 7. cut is more than 99.9%, and discharging at the bottom of tower is that modification extraction agent is circulated to azeotropic extraction rectifying tower, recycles.
The preferred processing condition of described sepn process are as follows: in sepn process, each tower reactor, tower top temperature control, reflux ratio, feed entrance point and stage number are shown in Table 1.
Table 1 sepn process processing condition
The present invention adopts the technique of azeotropic extraction rectifying and liquid liquid layering integrated purification sodium salt-DMF-toluene-water mixed solution, by traditional azeotropic distillation and extracting rectifying effective integration in the same apparatus, same azeotropic extraction rectifying tower realizes DMF, toluene is separated with water, simplify the technological process of production.Compared with traditional technology, the inventive method is by traditional azeotropic distillation and extracting rectifying effective integration, and adopt desalter to carry out preheating and desalination, in azeotropic extraction rectifying tower, realize multicomponent separation, technological process is simple; Adopt azeotropic extraction rectifying tower overhead vapours to raw material preheating, effectively utilize heat, reduce energy consumption; Adopt modification extraction solvent, significantly reduce the fusing point of extraction agent, when avoiding winter environment temperature low, on the impact of azeotropic extraction rectifying.Described method stock liquid is through azeotropic extraction rectifying and the primary treatment of liquid liquid stratified set apparatus for converting, and once can obtain toluene and more than 99.9% DMF of more than 99.5%, one time yield all reaches more than 98%, contains toluene lower than 0.08% after being separated in water.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of azeotropic extraction rectifying and liquid liquid layering integrated purification sodium salt-DMF-toluene-water mixed solution.
Embodiment
The method of azeotropic extraction rectifying of the present invention and liquid liquid layering integrated purification sodium salt, DMF, toluene and water mixed solution, tripping device and technical process are with reference to Fig. 1, and wherein 1 is azeotropic extraction rectifying tower, and 2 is desalter, 3 is azeotropic extraction rectifying tower well heater, 4 is feed preheater, and 5 is subcooling condenser, and 6 is venting hole, 7 is liquid liquid layering tank, 8 is condenser, and 9 is solvent reclamation recycle column, and 10 is well heater.
The sodium salt, DMF, toluene and the water mixed solution that adopt certain company to provide are raw material, the operation of azeotropic extraction rectifying tower is carried out at ambient pressure, tower internal diameter is 50mm, the Stainless Steel Helices of in-built φ 3*3 θ type, through measuring by standards system, this height equivalent to one theoretical plate HETP=27mm, tower reactor electric mantle heats, raw material, modification extractant feed and discharging are all with glass rotameter metering, and azeotropic extraction rectifying tower and solvent reclamation recycle column all adopt external reflux.
Sodium salt, DMF, toluene and water mixed solution 1. in feed preheater 4 through the preheating of azeotropic extraction rectifying tower 1 overhead vapours, and then by desalination evaporating pot 2 desalination, add in azeotropic extraction rectifying tower 1 by the middle and lower part of azeotropic extraction rectifying tower 1, azeotropic extraction rectifying tower 1 tower top, column bottom temperature is respectively 83.8 ~ 84.5 DEG C and 95.7 ~ 97.5 DEG C, 6. modification extraction agent (adds 15-20% dioctyl phthalate (DOP)) in the upper position charging of azeotropic extraction rectifying tower 1 in tetramethylene sulfone, 1. raw material is 1:0.4 ~ 1.0 with the ratio of modification extraction agent, 3. azeotropic extraction rectifying tower 1 tower top material is the mixing gas of toluene and water, after feed preheater 4 and subcooling condenser 5 raw material condensation and cryogenic condensation, tower top gas is condensed into liquid, fluid temperature≤20 DEG C, be divided in liquid liquid layering tank 7 toluene layer 4. with water layer 5., 4. toluene layer is more than 99.5% toluene, 5. water layer is the water (toluene is lower than 0.08%) of 99.9%, 8. azeotropic extraction rectifying tower 1 materials at bottom of tower is the mixed solution of modification extraction agent and DMF, solvent reclamation recycle column 9 sent into by tower reactor mixed solution, process through solvent reclamation recycle column 9, solvent reclamation recycle column 9 tower top distillates the DMF solution that 7. cut is more than 99.9%, materials at bottom of tower is modification extraction agent, be circulated to azeotropic extraction rectifying tower 1, recycle.
The processing condition of sepn process: in sepn process, each bottom temperature control, reflux ratio, feed entrance point and stage number are shown in Table 1.
Analyze through HP chromatographic instrument, raw material and each fractions consisting detailed results are shown in Table 2.
The separating resulting of the rectifying of table 2 azeotropic extraction and liquid liquid layering integrated purification sodium salt, DMF, toluene and water mixed solution
Claims (1)
1. a method for azeotropic extraction rectifying and liquid liquid layering integrated purification sodium salt, DMF, toluene and water mixed solution, comprises the following steps:
1) raw material sodium salt, DMF, toluene and water mixed solution are in massfraction, consist of sodium salt 0.1453, DMF0.1083, toluene 0.0269 and water 0.7195, described mixing solutions and azeotropic extractive distillation column overhead vapours carry out after heat exchange carries out preheating, again by the desalination of desalination evaporating pot, mixing solutions after desalination adds azeotropic extraction rectifying tower from the middle and lower part of azeotropic extraction rectifying tower, modification extraction agent adds in azeotropic extraction rectifying tower by the middle and upper part of azeotropic extraction rectifying tower, mixing solutions and modification extraction agent mass ratio are 1:0.4 ~ 1.0, described modification extraction solvent is the sulfolane solution containing 15 ~ 20wt% dioctyl phthalate (DOP), control tower top, column bottom temperature are respectively 83.8 ~ 84.5 DEG C and 95.7 ~ 97.5 DEG C, and mixing solutions is at azeotropic extraction rectifying tower through azeotropic extraction rectifying, and tower top obtains toluene and water mixing gas, obtains the mixture of DMF and modification extraction agent at the bottom of tower,
2) toluene and water mixing gas are after condensation, are divided into toluene layer and water layer, and toluene layer contains the toluene of 99.51wt%, water layer toluene level 0.05wt%; Toluene is partly refluxed to azeotropic extraction rectifying tower;
3) mixture of DMF and modification extraction agent is through solvent reclamation recycle column rectification process, and solvent reclamation recycle column tower top obtains the DMF of 99.83wt%, obtains modification extraction agent, be circulated to azeotropic extraction rectifying tower at the bottom of solvent reclamation recycle column tower.
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| CN104874196B (en) * | 2015-03-26 | 2016-09-14 | 南京师范大学 | A kind of method processing sodium and ammonium acetate salt-diazonium Organic substance-methanol-water mixed solution |
| CN105017054B (en) * | 2015-07-07 | 2017-01-11 | 天津大学 | Solvent recovering system for DMF (Dimethyl Formamide) saliferous wastewater |
| CN105348035B (en) * | 2015-12-15 | 2017-05-17 | 南京师范大学 | Method for integrated purification of chloroform and ethyl acetate mixed solution through azeotropic extractive distillation and liquid-liquid delamination |
| GB2551591B (en) | 2016-06-23 | 2019-08-07 | Tate & Lyle Tech Ltd | Liquid-liquid extraction of DMF |
| CN114276269A (en) * | 2021-12-29 | 2022-04-05 | 烟台国邦化工机械科技有限公司 | Recycling treatment method for wastewater in fiber production |
| CN115724708A (en) * | 2022-12-29 | 2023-03-03 | 南京长江江宇环保科技股份有限公司 | Method for separating toluene and N, N-dimethylformamide mixture |
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| CN101709025A (en) * | 2009-11-03 | 2010-05-19 | 南京师范大学 | Compound cross-flow liquid-liquid extraction separation method of methylal-methanol azeotropic system |
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| CN101709025A (en) * | 2009-11-03 | 2010-05-19 | 南京师范大学 | Compound cross-flow liquid-liquid extraction separation method of methylal-methanol azeotropic system |
| CN101734998A (en) * | 2009-12-22 | 2010-06-16 | 南京师范大学 | Method for extracting trimethylbenzene fraction in hydrocracking C9 by combined solvent extraction rectification method |
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