CN101921204B - Method for recycling DMAC (Dimethyl Acetylamide) from waste spandex stock solution - Google Patents
Method for recycling DMAC (Dimethyl Acetylamide) from waste spandex stock solution Download PDFInfo
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- CN101921204B CN101921204B CN201010249001.1A CN201010249001A CN101921204B CN 101921204 B CN101921204 B CN 101921204B CN 201010249001 A CN201010249001 A CN 201010249001A CN 101921204 B CN101921204 B CN 101921204B
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Abstract
The invention relates to a method for recycling DMAC (Dimethyl Acetylamide) from a waste spandex stock solution, comprising the following processes of: dividing a collected waste spandex stock solution into small blocks of 1-10 square centimeters, soaking the small blocks into deionized water, filtering and separating the mixture by a press filter to obtain a solid phase and a liquid phase, renewedly soaking the solid phase into a soaking pool, and repeating the operations many times; making the liquid phase and the ion liquid enter an extraction apparatus according to the mass rate of 1:0.5-3 to carry out mixed extraction, enriching DMAC in the mixed solution to the ion liquid phase to form an extraction phase containing the ion liquid and the DMAC as well as an extraction raffinate containing the deionized water and inorganic matters, making the extraction raffinate enter a rectifying apparatus, separating out the DMAC from the ion liquid phase with a method of decompression and distillation, and circularly recycling the ion liquid. In the invention, the method has the advantages of high recycling ratio of the DMAC and low energy consumption in the recycling process without causing secondary pollution.
Description
(1) technical field
The present invention relates to a kind of method that reclaims N,N-dimethylacetamide (DMAC) from the useless stoste of spandex.
(2) background technology
N,N-dimethylacetamide (DMAC) is a kind of strong aprotic, polar solvent, with N, dinethylformamide (DMF) is compared, and toxicity and the volatility of DMAC are lower, and stability is higher, not easy to change, be widely used in refining of petroleum and organic synthesis industry.DMAC has good solubility energy to various kinds of resin especially polyurethane resin, polyimide resin etc., can be used as the solvent of heat resistance fiber, plastics film, coating, pharmacy, catalyzer etc.
At present, in urethane elastic fiber production technology, major part is all to use DMAC as polymer solvent.In polyurethane fiber production process, due to polymerization stoste viscosity measurements sampling and release, stoste cleaning filter, filament spinning component throw before position release and the abnormal polymerization stoste producing of polymerization process etc. causes a large amount of spandexs stoste of giving up.In the useless stoste of spandex, contain 63～75% DMAC.This useless stoste, spandex manufacturer normally sells some with waste liquid and has the small business that processes the useless stoste of spandex, by they therefrom further purifying go out the DMAC that quality is lower, for leather, produce, or waste treatment.
At present, in industrial practice, for the useless stoste of spandex is general direct, by rectificating method, DMAC-water is separated, be called for short water law.Its shortcoming is that technological process energy consumption is high, meanwhile, is not suitable for containing DMAC and measures the useless stoste of low spandex.
Extraction-rectification combination technique is a kind of new DMAC wastewater processing technology, in molecular solvent, carry out, its technological process is first to adopt organic extractant that the DMAC in waste water is extracted in organic solvent, then realizes separation by DMAC and extraction agent by rectifying.The economical water law that is obviously better than of extraction-rectification combination technique, can process the DMAC waste water of lower concentration.But the method has the following disadvantages: have loss of extractant on the one hand, cause secondary pollution; Whole separation circuit is comprised of the upgrading tower of normal pressure and the passivation tower of decompression on the other hand, and complex procedures, consumes energy huge, and recovery cost is high, and decompression operation has increased the loss of solvent.
(3) summary of the invention
The object of the invention is to overcome above-mentioned deficiency, provide the rate of recovery of a kind of DMAC high, removal process energy consumption is low, can not cause the method that reclaims DMAC from the useless stoste of spandex of secondary pollution.
The object of the present invention is achieved like this: a kind of method that reclaims DMAC from the useless stoste of spandex, is characterized in that described method comprises following technological process:
Step 1, the useless stock solution water of spandex are processed and are separated
Useless the spandex of collection stoste is divided into and cuts the square fritter of 1～10cm, be immersed in deionized water, the mass ratio that feeds intake of the useless stoste of spandex and deionized water is 1: 0.5～10, soak 20～120 hours, by filtering obtain solid, liquid two-phase Fen Li with pressure filter, solid phase again drops into fermentation vat and soaks, and repeatedly, soak time and mass ratio are constant in repetitive operation;
Step 2, extraction
Step 1 is separated to the liquid phase and the ionic liquid 1: 0.5 in mass ratio～3 that obtain, with reflux type, enters in extraction equipment, carry out at normal temperatures and pressures hybrid extraction, the progression of extraction is 5～15 grades, make DMAC in mixing solutions be enriched to ionic liquid mutually in, the extraction phase that formation is comprised of extraction agent and DMAC and the extracting phase being formed by deionized water and inorganics
Step 3, rectifying
Step 2 is extracted to the extraction phase obtaining and enter rectifying device, by the method for underpressure distillation, isolate the DMAC of ionic liquid in mutually, ionic liquid cyclically utilizing,
Ionic liquid described in step 2 is the ionic compound consisting of a kind of positively charged ion and a kind of negatively charged ion, and its preparation method is as follows:
Methylimidazole and 3-chloropropyl ether were evenly mixed in 1: 1 in molar ratio, the 20-30 hour that refluxes in the water-bath of 85-95 ℃ under nitrogen protection, then removes unconverted reactant with silicone or ether washing, and rotary evaporation is removed silicone or ether.And then add and Methylimidazole or the equimolar Potassium Hexafluorophosphate (KPF of 3-chloropropyl ether
6), be heated to 85-95 ℃ and keep 15 hours, cooling, add deionized water wash dry, finally 85 ℃ of evaporations, within 10 hours, remove impurity, obtain ionic liquid.
Reaction formula is as follows:
(1)C
4H
6N
2+C
4H
9OCl→CH
3(C
3H
2N
2)
+CH
2CH
2CH
2OCH
3Cl
-
(2)CH
3(C
3H
2N
2)
+CH
2CH
2CH
2OCH
3Cl
-+KPF
6→
CH
3(C
3H
3N
2)
+CH
2CH
2CH
2OCH
3PF
6 -+KCl
The selection of ionic liquid of the present invention meets following character:
1) ionic liquid and DMAC complete miscibility, when ionic liquid and DMAC are when miscible, DMAC can enter ionic liquid phase completely, layering rapidly, starting time is short, without emulsion.
2) ionic liquid has significant hydrophobicity.Hydrophobicity makes the solvability of ionic liquid in water minimum, thereby reduces the loss of carrying secretly of extraction process intermediate ion liquid, and mass transfer velocity is fast simultaneously, is not easy to the secondary pollution that emulsification is carried secretly and bring thus.
3) ionic liquid has super dissolution characteristics, non-volatility, stable chemical property, can DMAC be separated with it by underpressure distillation.
The invention has the beneficial effects as follows:
The method adopts water to separate and press filtration isolation technique on the one hand, improves the extraction yield of the DMAC in useless spandex stoste; Utilize on the other hand ionic liquid as extraction agent, by the method for liquid-liquid extraction, DMAC extraction is reclaimed, stop the loss of extraction agent and cause secondary pollution.Whole process has that operation is simple, energy consumption is low, the rate of recovery is high and the advantage such as pollution-free.
(4) accompanying drawing explanation
Fig. 1 is that the useless stock solution water of spandex of the present invention is processed separation process scheme figure.
Fig. 2 is DMAC recovery process schema in the useless stoste of spandex of the present invention.
(5) embodiment
Referring to Fig. 1 and Fig. 2, Fig. 1 is that the useless stock solution water of spandex of the present invention is processed separation process scheme figure.Fig. 2 is DMAC recovery process schema in the useless stoste of spandex of the present invention.By Fig. 1 and Fig. 2, can be found out, from the useless stoste of spandex, reclaim the method for DMAC, comprise following technological process:
One, first prepare ionic liquid
Methylimidazole and 3-chloropropyl ether were evenly mixed in 1: 1 in molar ratio, the 20-30 hour that refluxes in the water-bath of 85-95 ℃ under nitrogen protection, then removes unconverted reactant with silicone or ether washing, and rotary evaporation is removed silicone or ether.And then add and Methylimidazole or the equimolar Potassium Hexafluorophosphate (KPF of 3-chloropropyl ether
6), be heated to 85-95 ℃ and keep 15 hours, cooling, add deionized water wash dry, finally 85 ℃ of evaporations, within 10 hours, remove impurity, obtain ionic liquid.
Two, from the useless stoste of spandex, reclaim DMAC
Step 1, the useless stock solution water of spandex are processed and are separated
As shown in Figure 1, useless the 100Kg spandex of collecting stoste (mass percent 67.3%) is divided into and cuts the square fritter of 1～10cm and be immersed in the fermentation vat that contains deionized water, in fermentation vat, the mass ratio of the useless stoste of spandex and deionized water is 1: 1, soak and by filter, filter after 24 hours, collect filtrate (packing the standby extraction of filtrate tank into uses) and filter residue, filter residue again drops into fermentation vat and soaks, twice of repetitive operation, soak time and mass ratio are constant, finally by filter residue through pressure filter press filtration, collect filtrate enter filtrate tank.The mass percent that detects DMAC solution in filtrate tank is 20.84%.The useless stoste of spandex is after repeatedly deionized water soaks, and in the useless stoste of spandex, the percentage extraction of DMAC reaches 98.92%.
Step 2, extraction
As shown in Figure 2, step 1 is separated to the liquid phase and the ionic liquid 1: 1 in mass ratio that obtain, with reflux type, enters in extraction equipment (Multistage tower-type settler), carry out at normal temperatures and pressures hybrid extraction, filtrate enters from the light phase entrance of next stage, extraction agent enters from the heavy liquid inlet of upper level, and 10 stage countercurrents extractions occur mixing solutions under device stirring action.Mixing solutions enters settling section, forms two-phase, i.e. extraction phase and extracting phase, after counter-current extraction step by step, DMAC transfers in extraction phase, and last extraction phase is discharged and entered rectifying tower rectifying from the heavy out of next stage, and extracting phase is discharged and added fermentation vat by the light phase export of upper level.After testing in extracting phase DMAC concentration lower than 100ppm.
Step 3, rectifying
Step 2 is extracted to the extraction phase obtaining and enter rectifying device (Multistage tower-type settler), adopt underpressure distillation, DMAC with gas phase form from side line extraction, after condensation, obtain purity and reach 99.9% DMAC liquid, water ratio is lower than 100ppm, the solution polymerization dry-spinning that can be used for spandex, the rate of recovery can reach 99.5%.Ionic liquid cyclically utilizing.
Claims (1)
1. a method that reclaims DMAC from the useless stoste of spandex, is characterized in that described method comprises following technological process:
Step 1, the useless stock solution water of spandex are processed and are separated
Useless the 100Kg spandex of the mass percent of collection 67.3% stoste is cut into the square fritter of 1～10cm to be immersed in the fermentation vat that contains deionized water, in fermentation vat, the mass ratio of the useless stoste of spandex and deionized water is 1: 1, soak and by filter, filter after 24 hours, collect filtrate and filter residue, filter residue again drops into fermentation vat and soaks, twice of repetitive operation, soak time and mass ratio are constant, finally by filter residue through pressure filter press filtration, collect filtrate and enter filtrate tank, the mass percent that detects DMAC solution in filtrate tank is 20.84%, the useless stoste of spandex is after repeatedly deionized water soaks, in the useless stoste of spandex, the percentage extraction of DMAC reaches 98.92%,
Step 2, extraction
Step 1 is separated to the liquid phase that obtains and ionic liquid 1: 1 in mass ratio, with reflux type, enter in extraction equipment Multistage tower-type settler, carry out at normal temperatures and pressures hybrid extraction, filtrate enters from the light phase entrance of next stage, extraction agent enters from the heavy liquid inlet of upper level, under device stirring action, there are 10 stage countercurrent extractions in mixing solutions, mixing solutions enters settling section, form two-phase, be extraction phase and extracting phase, after counter-current extraction step by step, DMAC transfers in extraction phase, last extraction phase is discharged and is entered rectifying tower rectifying from the heavy out of next stage, extracting phase is discharged and is added fermentation vat by the light phase export of upper level, after testing in extracting phase DMAC concentration lower than 100ppm,
Step 3, rectifying
Step 2 is extracted to the extraction phase obtaining and enter rectifying device Multistage tower-type settler, adopt underpressure distillation, DMAC with gas phase form from side line extraction, after condensation, obtain purity and reach 99.9% DMAC liquid, water ratio is lower than 100ppm, for the solution polymerization dry-spinning of spandex, the rate of recovery reaches 99.5%, ionic liquid cyclically utilizing.
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| CN103600437B (en) * | 2013-11-08 | 2015-12-02 | 顾社辉 | The integrated conduct method of dry spinning spandex waste material |
| CN110016730B (en) * | 2019-05-05 | 2021-09-03 | 华峰化学股份有限公司 | Method for processing and spinning spandex aqueous waste stock solution |
| CN110078285A (en) * | 2019-05-08 | 2019-08-02 | 徐州工程学院 | A kind of Urethane Elastic Fibre Industrial Wastewater efficient treatment process |
| CN110423192A (en) * | 2019-08-14 | 2019-11-08 | 郑州中科新兴产业技术研究院 | A kind of recovery method of spandex DMAC/ acetic acid organic liquid waste |
| CN114516816B (en) * | 2022-02-24 | 2023-12-01 | 深圳瑞华泰薄膜科技股份有限公司 | Method and device for recycling DMAC and isoquinoline from solution |
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| CN1594116A (en) * | 2003-09-08 | 2005-03-16 | 中国科学院过程工程研究所 | Process for separating and recovering minim organic solvent from waste water using ion liquid |
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