CN102190611B - Method for purifying N-methyl pyrrolidone and gamma-butyrolactone - Google Patents
Method for purifying N-methyl pyrrolidone and gamma-butyrolactone Download PDFInfo
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- CN102190611B CN102190611B CN2011100820191A CN201110082019A CN102190611B CN 102190611 B CN102190611 B CN 102190611B CN 2011100820191 A CN2011100820191 A CN 2011100820191A CN 201110082019 A CN201110082019 A CN 201110082019A CN 102190611 B CN102190611 B CN 102190611B
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Abstract
The invention discloses a method for purifying N-methyl pyrrolidone and gamma-butyrolactone, which comprises the following steps of: making a reagent to be purified pass through a polystyrene-divinylbenzene type nonpolar macroporous resin column, filtering by using a charged cellulose membrane, and performing rough filtration and fine filtration on filtrate in turn by using polytetrafluoroethylene filters in different dimensions. The method has the advantages of simple process, easily controlled conditions, low energy consumption, no rigorous requirement on power equipment, no need of special temperature control conditions and effective production under conventional temperature, and is used for recovering and purifying the N-methyl pyrrolidone and the gamma-butyrolactone, and the purity of the obtained reagent can reach an electron level; meanwhile, materials such as the macroporous resin can be used as fuel to be reutilized, and are light in environmental pollution; and the process has a larger application space and good market prospect.
Description
Technical field
The present invention relates to the method for purification of N-Methyl pyrrolidone and gamma-butyrolactone.
Background technology
Along with the fast development of advancing by leaps and bounds of science and technology, particularly electron trade, just need more, more highly purified electronic chemical products; These high pure electronic chemical mainly are divided into organic and inorganic two big types; The high-purity chemicals of present domestic inorganic acids is comparatively common, and it is ripe that technology also is tending towards gradually, but the almost whole dependence on import of organic solvent class high-purity chemicals; And core technology is monopolized a feasible big bottleneck that becomes the electron trade development of restriction China by external.According to international semiconductor employer's organization requirement; The high pure electronic chemical has all proposed strict demand to several aspects such as purity, moisture, ion content, fine grain level and pH respectively; Its ions content and fine grain level are the bottleneck problems of such high-purity chemicals of restriction; At present the multipotency of domestic technique reaches the SEMI C-7 standard that international semiconductor employer's organization formulates, and the newest standards SEMI Grade5 that formulates with international semiconductor employer's organization also has very big distance.
N-Methyl pyrrolidone (NMP) and gamma-butyrolactone (GBL) are semicon industry two kinds of organic solvents commonly used.Wherein N-Methyl pyrrolidone (being called for short NMP) is mainly used in the electrolytic solution of lithium ion battery; Clean-out system in electronic product productions such as precision instrument, liquid-crystal display, hard disk, magnetic head and the maintenance process; High-end fields such as the stripping liquid of photoresist disk, and gamma-butyrolactone (GBL) mainly is used as the electrolytic solution of lithium ion battery, along with the lack of energy phenomenon is serious day by day in recent years; The lithium cell industry obtains fast development; China has become the maximum export State of whole world lithium ion battery at present, and export volume and amount of money rank prostatitis are as electrolytic solution and electrode subsidiary material in lithium ion battery is made; Its demand increases rapidly, annual NMP at the consumption in this field above 1.3 ten thousand tons; In addition, the consumption of the NMP that uses as the positive electrode material of automobile power cell also can sharply increased in recent years.Add the fast development of plasma LCD TV and electronic information industry; Particularly India's electronic industry undergoes an unusual development rapidly; And Chongqing is about to make Chinese the third-largest electronic product processing base, along with the progressively enforcement of these a series of strategic plans, as employed solvent or clean-out system in the electronic product manufacturing processed; Its consumption will certainly rapidly increase in the coming years, and this just provides a good development opportunity for electronic-grade NMP.But the NMP as electronic-grade is not only very high to the requirement of purity; Moisture, metal ion content, fine grain level and pH value all there is strict control; These impurity are handled electronic product quality of influence and work-ing life directly; Lithium ion battery as producing with electronic-grade NMP is not easy generation " puncture " phenomenon because metal ion content is low, thereby adds the work-ing life that no dust granules has prolonged battery greatly.In line with the endless principle of quality-improving; World semiconductor employer's organization has formulated the SEMI standard; According to this standard; Use the integrated level of the chip that the reagent that meets SEMI C-7 standard produces to be 1-4M, and the integrated level of the chip of producing with the reagent that meets SEMI Grade 5 standards is greater than 64G, so the high pure electronic grade chemical is expensive more a lot of than common technical grade chemical.The content of domestic electronic-grade NMP that produces and GBL product requirement metals ion is less than 10ppb at present; And NMP is good organic solvent; Solvability to a lot of materials of occurring in nature is all very strong, and the rectifying temperature is higher, if select the general not anti-high temperature of the rectifying tower that gathers the tetrafluoro material for use; The equipment heat-transfer effect is relatively poor and cause temperature also wayward, and facility investment simultaneously is high; If adopt the equipment of stainless steel will certainly introduce little metal impurity, and the both exists because the solid dust particle content problem of higher that the starting material factor is brought into.
Present domestic NMP mainly is divided into four grades such as technical grade, aramid fiber level, electronic-grade and SILVER REAGENT; Wherein electronic-grade and SILVER REAGENT require product purity to reach 99.9%, moisture content 300ppm, various metal ion contents are less than 10ppb; Various anion-contents are less than 0.5ppm; The standard-required fine grain level of formulating according to international semiconductor association in addition 25/L, pH and can reach requirement through product purity, moisture content, anion-content and pH value with stainless steel rectifying basically between 7-9; Metal ion content and particulate number but can not reach requirement, and this just becomes a bottleneck problem of the high-purity organic electronic chemical development of restriction.And along with lack of energy; The organic solvent that is recycled is more and more; The requirement of how the organic solvent product quality that reclaims being brought up to electronic-grade also becomes a difficult problem, and this just just becomes a domestic problem that needs to be resolved hurrily for the requirement that promotes the product quality of organic solvent fast and efficiently and then reach electronic-grade.
Summary of the invention
One of the object of the invention is to overcome above-mentioned defective, and the method for purification of a kind of N-Methyl pyrrolidone and gamma-butyrolactone is provided, and technology is simple; Condition is prone to control; Energy consumption is low, is used for reclaiming and purification N-Methyl pyrrolidone and gamma-butyrolactone, and the purity of gained reagent can reach electronic-grade.
The method of purification of said N-Methyl pyrrolidone of the present invention and gamma-butyrolactone comprises the steps:
A. reagent to be purified is crossed the non-polar macroporous resin post, use the plain membrane filtration of charged fiber then, must filtrate, said macroporous resin is mixed by weight ratios such as polystyrene-divinylbenzene type resin anion(R.A) and polystyrene-divinylbenzene type resin cation(R.C.)s;
B. get filtrating and, get the reagent of required purity with the smart filter of polytetrafluoroethylene filter.
Because its purity of reagent of electronic product, moisture, pH value and colourity require very strict; And two kinds of agent dissolves property of N-Methyl pyrrolidone and gamma-butyrolactone are very strong, the material of therefore in purification process, selecting for use at first will to organic solvent have inertia, material itself colourless, can not contain moisture, can not change the pH value of stoste.Researchist of the present invention is through screening conventional resin of kind more than 20 and unconventional resin; And contrast the adsorption effect of various resins to metals ion; It is better that the large pore gel resin of confirming the polystyrene-divinylbenzene type is treated two kinds of reagent unreactivenesses of purification; Can not increase colourity, pH value and the moisture content etc. of solvent; Said resin weight ratio such as is pressed by polystyrene-divinylbenzene type resin anion(R.A) and polystyrene-divinylbenzene type resin cation(R.C.) and is mixed, and after reagent was crossed resin column, the pH value can not change.
Further, before reagent to be purified is crossed said macroporous resin column among the step a, macroporous resin is carried out pre-treatment, comprise the steps:
1. get said resin anion(R.A) and resin cation(R.C.), soak elimination moisture respectively with deionized water; Under agitation condition, use the HCl solution soaking earlier again, use the NaOH solution soaking again, extremely neutral with the ultrapure water washing at last;
2. repeating step operation 1. is 2-3 time;
3. under agitation condition; With 2. gained resin anion(R.A) of carbonic acid soln soaking step,, use two kinds of resins of deionized water rinsing again to neutrality with 2. gained resin cation(R.C.) of ammonia soln soaking step; Continue flushing 2-3h, drop anhydrate branch and in 30-60 ℃ of temperature vacuum-drying to constant weight;
4. weight ratios such as dried resin anion(R.A) and resin cation(R.C.) are mixed, get macroporous resin.
Owing to the new macroporous resin overwhelming majority of buying is directly from industrial production, to prepare, self have some impurity, for example have common metal ion such as potassium, sodium, calcium, magnesium, the phenomenon of the metals ion stripping that meeting generation resin carries in the purification process; And high-purity resin price is higher relatively, and a large amount of economic rationalities of using are on the low side, and macroporous resin is carried out pre-treatment, remove the impurity and the water-soluble metal ion of trace in the resin, reduce the dissulution and the fine solid particle PM for particulate matter of metals ion.
Simultaneously, because electronic-grade NMP or GBL product requirement moisture is less than 100ppm, colourity is less than 15; Therefore pretreated macroporous resin also needs drying treatment; The present invention studies confirmation, and vacuum-drying does not have influence to the colourity of resin under 30-60 ℃ of temperature, when temperature is higher than 60 ℃; Dried resin colourity can increase to some extent, can cause the colourity of reagent treatment to increase thereupon.After the drying, under 150 ℃ of temperature, detect not water outlet branch with Ka Shi stove moisture content tester and be advisable.
Further, the 1. middle HCl liquid quality fraction of step is 1-10%, and the NaOH liquid quality fraction is 1-10%, and the step 3. massfraction of middle carbonic acid soln is 1-10%, and the ammonia soln massfraction is 1-10%.
Further, among the step a, the reagent of waiting to purify descended said macroporous resin column in room temperature-60 a ℃ condition, and crossing column flow rate is PM 1/50-1/10 times of resin volume.
In room temperature-60 ℃ scope, temperature is little to the influential effect of resin absorption metals ion, is higher than 60 ℃ the colourity of filtering the back nmp solution is increased; Flow velocity with PM 1/50-1/10 times of resin volume all can, the best is a PM 1/35-1/25 times of resin volume, is higher than this flow velocity adsorption effect and obviously descends, the increase that is lower than this flow velocity adsorption effect is very little.
Further, among the step a, the plain film of said charged fiber is obtained by following steps:
(1) the preparation quality mark is the SDS-polyacrylamide gel of 10-15% and puts into electrophoresis chamber; In electrophoresis chamber and sample introduction groove, inject the Tris-HCl damping fluid of pH=8.4 again; The protein solution that with the massfraction is 5-25% is a sample feeding; In 200-300V, the galvanic effect lower running plate of 10-30mA, close electrophoresis apparatus behind the 0.5-2.5h, get the electrophoresis film;
(2) soak electrophoresis film 12-36h post-flush 0.5-3h with deionized water, again in 30-50 ℃ of forced air drying to constant weight, wafer;
(3) wafer is ground into the powder of 10-150 μ m granularity in electrostatic field, adds dispersion agent then and mix;
(4) evenly be coated between the two-layer CAM step (3) gained material and compressing tablet, get double-deck charged cellulose acetate film.
Though reagent contained amount of metal ion after macroporous resin treatment significantly reduces; But owing to usually carry a spot of metals ion secretly in macroporous resin itself and the production process; Make after the macroporous resin treatment; The reagent metal ion content can't reach the electronic-grade requirement, so adopts the plain film of charged fiber to remove the impurity metal ion of trace in the solution among the present invention, plays the effect of solid particulate matter being carried out coarse filtration simultaneously.
Further; Said FM membrane pore size is 0.2-0.8 μ m, can also effectively remove solid particulate matter when effect is the adsorb traces metals ion, plays the effect of a coarse filtration; Thereby can save this step of coarse filtration, further simplify processing technological flow.
Further, said electrostatic field intensity is 2-12V, and galvanic negative pole is connected with the electrical conductor of kibbler section with all contact materials, further increases the electrically charged amount of charged particle.Cross strong electrostatic field and may damage or damage kibbler, be not easy to manual operation, cross weak current and do not have the charged effect of enhancing electrified body human body.
Beneficial effect of the present invention is: the method for purification of N-Methyl pyrrolidone provided by the invention and gamma-butyrolactone has the advantage that technology is simple, condition is prone to control; Be easy to realize industriallization; Production capacity that can existing apparatus is designed to according to enlarging production in proportion by existing lab setup, and energy consumption is low, and power-equipment is not had harsh requirement; Need not special temperature control condition; Under conventional temperature, can realize effective production, be used for reclaiming and purification N-Methyl pyrrolidone and gamma-butyrolactone that the purity of gained reagent can reach electronic-grade; Simultaneously can be used as fuel feedback such as materials such as macroporous resins, environmental pollution is little; Technology of the present invention has bigger adaptation space and good market outlook.
Embodiment
Below in conjunction with specific embodiment the object of the invention, technical scheme and advantage are further specified, should be appreciated that embodiment only is used to the present invention is described and unrestricted.
Embodiment:
1, gets polystyrene-divinylbenzene type resin anion(R.A) and polystyrene-divinylbenzene type resin cation(R.C.); Respectively with deionized water soak 12h (here soak time 12-36h all can); Elimination moisture, again under agitation condition, using massfraction earlier is that 4% HCl solution (top grade is pure) soaks two kinds of resin 2h respectively; Using massfraction again is that 4% NaOH solution (top grade is pure) soaks two kinds of resin 2h respectively, at last with the ultrapure water washing to neutral; Repeat aforementioned operation 2 times; Again under agitation condition; The use massfraction is 4% carbonic acid soln (top grade is pure) immersion gained resin anion(R.A) 6h; The use massfraction is 4% ammonia soln (top grade is pure) immersion gained resin cation(R.C.) 5h; Use two kinds of resins of deionized water rinsing then to neutrality, continue flushing 2h, the drop branch that anhydrates.In this step, the massfraction of the massfraction of the massfraction of HCl solution, NaOH solution, the massfraction of carbonic acid soln and ammonia soln can be between 1-10%, and preferably 4%-6%.
2, resin anion(R.A) after the purifying treatment and resin cation(R.C.) are placed vacuum drying oven, vacuum-drying to Ka Shi stove moisture content tester (Switzerland, Metrohm 841) is till detecting not water outlet branch under 150 ℃ of temperature under 55 ℃ of temperature; Need to prove; Vacuum-drying temperature here between 30-60 ℃, such as 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ equitemperatures all can, optimum temperature range is 45 ℃-55 ℃; Drying efficiency is high, and the resin proterties is stable.
3, weight ratios such as dried resin anion(R.A) and resin cation(R.C.) are mixed; Pour chromatography column (35*600mm CD-0221 type into; Shanghai Chu setting analysis Instr Ltd.) in; Get three parts of former fluid samples of N-Methyl pyrrolidone again, make its liquid temperature keep 25 ℃ (being room temperature) to descend post respectively, crossing column flow rate is 1/35 times of resin volume of PM.
Three parts of former fluid samples are numbered 1#NMP stoste, 2#NMP stoste and 3#NMP stoste respectively; Handle gained reagent and do gc (Varian GC 450) purity check, atom absorption spectrophotometry appearance (Hitichi z-2000) analysis and ultraviolet (Hitichi UV 3010) scanning; Ultra-violet analysis shows does not have the redundant impurities peak to occur; The purity check analytical data is as shown in table 1, and the content results of four kinds of common metal ion is as shown in table 2 in the atom absorption spectrophotometry appearance mensuration nmp solution:
450 pairs of nmp solution purity check of table 1 Varian GC result
| The sample title | BLO（%） | NMP（%） | NMS（%） | 5-NMP(%) |
| The NMP stoste of filtered | 0.01 | 99.96 | 0.02 | 0.01 |
| With the nmp solution behind the resin filter | 0.01 | 99.96 | 0.02 | 0.01 |
Table 2 atom absorption spectrophotometry appearance is to the mensuration result of metals ion in the nmp solution
The experimental data of table 1 shows: this resinoid is insoluble to nmp solution, can not introduce other impurity with this type of resin filter nmp solution; And the experimental data of table 2 can find out that this workshop section can remove the common metal ion more than 80% effectively, and the result who detects with chromatography of ions shows with this type of resin filter nmp solution can also reduce anionic content in the solution a little.
In step 3; Liquid temperature when the contriver also changes stoste and crosses post (the liquid temperature is adjusted into 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ respectively when crossing post); Under the situation of other operating parameters unanimity, investigated of the influence of post liquid temperature to the treatment effect of stoste, confirm that the liquid temperature remains in the room temperature-60 ℃ scope; The liquid temperature is little to the influential effect of resin absorption metals ion, and being higher than 60 ℃ can influence the colourity that is processed reagent.
In step 3; The present invention has investigated under other operating parameters uniform condition simultaneously; Cross under the condition of column flow rate different (being specially 1/50 times of PM, 1/45 times, 1/40 times, 1/30 times, 1/25 times, 1/20 times, 1/15 times, 1/10 times resin volume); To the influence of the effect of resin absorption metals ion, the result show flow velocity PM 1/50-1/10 times of resin volume range all can, be good with PM 1/35-1/25 times of resin volume; Be higher than this flow velocity adsorption effect and obviously descend, the increase that is lower than this flow velocity adsorption effect is very little.
4, the preparation massfraction be 12.5% SDS-polyacrylamide gel film (please with reference to Laemmli U K. Cleavage of structural proteins during the assembly of the head of bacteriophage T4 [J]. Nature 1970; 227:680-685. diplomatic method prepares running gel); The gained gel film is placed in the electrophoresis chamber; The Tris-HCl damping fluid that injects pH=8.4 is as moving phase; In 15% the egg protein solution sample injection sample cell, go up 200-300V, the galvanic effect lower running plate of 10-30mA in vertical slab electrophoresis appearance (DYCZ-24DN type, Liuyi Instruments Plant, Beijing) then again; Close electrophoresis apparatus behind the 1h and take out running gel, get running gel with blade excision 5cm bottom, top 3cm film (according to repeatedly with resulting empirical value behind the coomassie brilliant blue staining).Certainly, in this step, SDS-polyacrylamide gel massfraction all can between 10-15%.
5, the gained running gel is soaked 24h with deionized water after; (forced air drying temperature here all can at 30-50 ℃ in 40 ℃ of temperature drying to constant weights in the air dry oven with being placed on behind the mobile deionized water rinsing 1h; For example can be 35 ℃, 45 ℃ etc.), film.
6, film is used have the fine-powder that is ground into 10-150 μ m size in the submicron ultrafine crusher (grand machine works is assisted in Shenzhen) of electrostatic field intensity as 6V; Then fine-powder evenly is coated in the cellulose acetate film (Whatman in 0.45 μ m aperture; Britain) on; And then covering the same CAM of one deck in the coating opposite side, compressing tablet makes double-deck charged cellulose acetate film.
7, with the special film fixture of the double-deck charged cellulose acetate film of the gained polytetrafluoroethylmaterial material that to be fixed on an internal diameter be 10cm; Be to filter aforementioned NMP reagent after macroporous resin treatment under the condition of 5ml/min at room temperature (25 ℃), flow velocity; Must filtrate, gained filtrating is used ICP-MS X
2Metal ion content in Series (Therm-Fisher, the U.S.) the cool flame mode detection nmp solution, 1 experimental result is as shown in table 3 below.
Each item index of 1#NMP sample contrast before and after table 3 is handled
Table 3 is the result show: can be through this kind filtration so that GOLD FROM PLATING SOLUTION belongs to ionic content to be reduced to below the 10ppb, and part element even can be reduced to below the detectability.In addition, because the aperture of double-deck cellulose membrane is 0.45 μ m, so this step also has a function of solid particulate matter being carried out coarse filtration.
8, adopt the polytetrafluoroethylene filter (3M of 0.1 μ m specification; The U.S.) smart filter step 7 gained filtrating; To reduce the fine grain level in the reagent, because the property of two kinds of solvents makes that the contriver carries out immersion test through the filter membrane to unlike material to the very strictness of requirement of filtering material; The strainer that confirms polytetrafluoroethylmaterial material has unreactiveness to two kinds of materials; After coarse filtration and smart filter processing, the PM for particulate matter level in the product promptly reaches the requirement of electronic-grade, meets the standard of the SEMI C-7 of international semiconductor association.
The operation of repeating step 1-8, (GBL) reclaims purification to gamma-butyrolactone, and concrete data are following:
Conclusion:
Technology according to the invention can be carried out in an airtight flow path system, and all link pipelines all adopt polytetrafluoroethylmaterial material, avoid causing external contamination; Whole flow process is easy to industriallization; Production capacity with existing apparatus is designed to get final product according to enlarging in proportion by existing lab setup, can also make full use of the advantage of existing apparatus, and the NMP product that existing apparatus is produced directly adopts this technology to purify; Need not increase any power-equipment; Need not special temperature control conditioned disjunction temperature controlling system, energy consumption is low, under conventional temperature, can realize effective production; Be used for reclaiming and purification N-Methyl pyrrolidone and gamma-butyrolactone, the purity of gained reagent can reach electronic-grade; Simultaneously can be used as fuel feedback such as materials such as macroporous resins, environmental pollution is little; Straining installation can be through reaching the regenerated purpose with the organic solvent recoil, and the used waste liquid that recoils can directly be refunded original device and carried out rectification and purification, and not only save energy also helps low-carbon environment-friendly.Simultaneously, this technology also has good versatility, can be extended in the preparation of high-purity organic solvents such as THF, has bigger extending space and good market outlook.
Claims (5)
1.N-the method for purification of SL 1332 or gamma-butyrolactone is characterized in that: comprise the steps:
A. after will reagent purified crossing the non-polar macroporous resin post,, must filtrate with the plain membrane filtration of charged fiber; Said macroporous resin is mixed by weight ratios such as polystyrene-divinylbenzene type resin anion(R.A) and polystyrene-divinylbenzene type resin cation(R.C.)s;
B. get filtrating and, get the reagent of required purity with the smart filter of polytetrafluoroethylene filter;
Before reagent to be purified is crossed said macroporous resin column among the step a, macroporous resin is carried out pre-treatment, comprise the steps:
1. get said resin anion(R.A) and resin cation(R.C.), soak elimination moisture respectively with deionized water; Under agitation condition, use the HCl solution soaking earlier again, use the NaOH solution soaking again, extremely neutral with the ultrapure water washing at last;
2. repeating step operation 1. is 2-3 time;
3. under agitation condition; With 2. gained resin anion(R.A) of carbonic acid soln soaking step,, use two kinds of resins of deionized water rinsing again to neutrality with 2. gained resin cation(R.C.) of ammonia soln soaking step; Continue flushing 2-3h, drop anhydrate branch and in 30-60 ℃ of temperature vacuum-drying to constant weight;
4. weight ratios such as dried resin anion(R.A) and resin cation(R.C.) are mixed, get macroporous resin;
Among the step a, the plain film of said charged fiber is obtained by following steps:
(1) the preparation quality mark is the SDS-polyacrylamide gel of 10-15% and puts into electrophoresis chamber; In electrophoresis chamber and sample introduction groove, inject the Tris-HCl damping fluid of pH=8.4 again; The protein solution that with the massfraction is 5-25% is a sample feeding; In 200-300V, the galvanic effect lower running plate of 10-30mA, close electrophoresis apparatus behind the 0.5-2.5h, get the electrophoresis film;
(2) soak electrophoresis film 12-36h post-flush 0.5-3h with deionized water, again in 30-50 ℃ of forced air drying to constant weight, wafer;
(3) wafer is ground into the powder of 10-150 μ m granularity in electrostatic field, adds dispersion agent then and mix;
(4) evenly be coated between the two-layer CAM step (3) gained material and compressing tablet, get double-deck charged cellulose acetate film.
2. the method for purification of N-Methyl pyrrolidone according to claim 1 or gamma-butyrolactone; It is characterized in that: the 1. middle HCl liquid quality fraction of step is 1-10%; The NaOH liquid quality fraction is 1-10%; The step 3. massfraction of middle carbonic acid soln is 1-10%, and the ammonia soln massfraction is 1-10%.
3. the method for purification of N-Methyl pyrrolidone according to claim 2 or gamma-butyrolactone is characterized in that: among the step a, the reagent of waiting to purify descended said macroporous resin column in room temperature-60 a ℃ condition, and crossing column flow rate is PM 1/50-1/10 times of resin volume.
4. according to the method for purification of each described N-Methyl pyrrolidone of claim 1 to 3 or gamma-butyrolactone, it is characterized in that: said FM membrane pore size is 0.2-0.8 μ m.
5. the method for purification of N-Methyl pyrrolidone according to claim 4 or gamma-butyrolactone is characterized in that: said electrostatic field intensity is 2-12V.
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| CN103058910B (en) * | 2013-01-21 | 2014-09-17 | 郑州大学 | Separation method of organic amine impurity in N-methyl pyrrolidinone |
| CN110551051B (en) * | 2019-09-19 | 2021-10-29 | 山东长信化学科技股份有限公司 | Method for reducing metal ion content and granularity by N-methyl pyrrolidone |
| CN111269163B (en) * | 2020-03-19 | 2022-11-29 | 江苏盈天环保科技有限公司 | Method for removing gamma butyrolactone in N-methyl pyrrolidone |
| CN112939838A (en) * | 2021-02-10 | 2021-06-11 | 绵阳艾萨斯电子材料有限公司 | NMP waste liquid purification method and system |
| CN114181130B (en) * | 2021-12-16 | 2022-09-20 | 浙江联盛化学股份有限公司 | Purification method of N-methyl pyrrolidone |
| CN115304532B (en) * | 2022-07-27 | 2023-06-06 | 江西盛源新材料有限公司 | Purification method of N-methyl pyrrolidone |
| CN115999652A (en) * | 2022-12-29 | 2023-04-25 | 徐州博康信息化学品有限公司 | Method for removing metal impurities from parahydroxystyrene copolymer resin containing acetal protective structure |
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| CN1712396A (en) * | 2005-04-13 | 2005-12-28 | 广东工业大学 | Gas-phase production of N-hydroxyethyl-pyrrolidone |
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