CN113429329A - Purification method of semiconductor grade N-methyl pyrrolidone - Google Patents
Purification method of semiconductor grade N-methyl pyrrolidone Download PDFInfo
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- CN113429329A CN113429329A CN202110760811.1A CN202110760811A CN113429329A CN 113429329 A CN113429329 A CN 113429329A CN 202110760811 A CN202110760811 A CN 202110760811A CN 113429329 A CN113429329 A CN 113429329A
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 title claims abstract description 43
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 11
- 238000000746 purification Methods 0.000 title abstract description 7
- 239000012528 membrane Substances 0.000 claims abstract description 26
- 238000005374 membrane filtration Methods 0.000 claims abstract description 20
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- 239000000047 product Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 239000002808 molecular sieve Substances 0.000 claims abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 7
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 6
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 5
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 5
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 5
- 229960004853 betadex Drugs 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- 239000012982 microporous membrane Substances 0.000 claims abstract description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 22
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003729 cation exchange resin Substances 0.000 claims description 16
- 239000003957 anion exchange resin Substances 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- 238000005342 ion exchange Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- SKYXZSVBBFFJQQ-UHFFFAOYSA-N 1-methyl-2h-pyrazine Chemical compound CN1CC=NC=C1 SKYXZSVBBFFJQQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000001471 micro-filtration Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
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- 229910021645 metal ion Chemical group 0.000 description 11
- 238000001914 filtration Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- -1 alkali metal salt Chemical class 0.000 description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 238000013094 purity test Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Pyrrole Compounds (AREA)
Abstract
The invention discloses a purification method of semiconductor grade N-methyl pyrrolidone, which takes industrial grade-methyl pyrrolidone as a raw material, and comprises the steps of pretreating, adsorbing and dehydrating by a 4A molecular sieve, respectively carrying out membrane filtration twice by a beta-cyclodextrin composite membrane and a 18-crown-6 composite membrane, carrying out reduced pressure rectification on filtrate, condensing collected fractions, and carrying out grade membrane filtration by a microporous membrane to prepare a target product. The content of N-methyl pyrrolidone obtained by the method of the invention reaches 99.9%, and the water content, the cation content and the anion content all accord with the 12-grade standard of chemical materials established by international semiconductor equipment and material organization, and the method can be used for the aspects of cleaning, drying and the like in the processes of assembling and processing semiconductors and large-scale integrated circuits.
Description
Technical Field
The invention relates to the technical field of chemistry, in particular to a purification method of semiconductor grade N-methyl pyrrolidone.
Background
N-methyl pyrrolidone is a fine chemical with excellent performance, has strong dissolving capacity for polar or non-polar substances due to the strong dissolving capacity, is called as a universal solvent, and is widely used in the industrial fields of coatings, printing ink, electronic chemicals, high-grade cleaning agents, power lithium ion batteries and the like as a solvent or an organic raw material.
The problem of the desorption of N-methyl adjacent pyrrolidone and metal ions is widely concerned, and for the problem of the desorption of the N-methyl adjacent pyrrolidone, CN101696182A is to adsorb and desorb the N-methyl adjacent pyrrolidone to be purified through a molecular sieve column, and is limited by the limitation of adsorption speed and adsorption capacity, and the treatment amount is only 0.4 to 0.8 liter/hour; CN200910064504.9 discloses a purification method of N-methyl pyrrolidone for producing liquid crystal panels, wherein a water-blocking agent is added into raw material N-methyl pyrrolidone, and then the raw material N-methyl pyrrolidone enters a three-tower component refining and regressing system to continuously reduce pressure, and the purity of the prepared product is more than 99.9%, and the water content is less than 0.01%.
For removing impurity metal ions in N-methyl pyrrolidone, U.S. Pat. No. 4,989,370 removes the impurity metal ions by adding alkali metal or alkali metal salt, and then obtains high-purity NMP by continuous step-by-step refining; CN110551051A discloses a method for removing metal ion content and granularity, which is a technology for preparing N-methyl pyrrolidone by aminating monomethylamine and Y-butyrolactone (GBL), wherein the most critical metal ion particle removal is in the control stage of filtration and demagnetization in the last step, but the requirements of updating or reactivating the fiber after the filtration are not repeated; the preparation method of CN108299266A high-purity N-methyl pyrrolidone discloses a method for removing water in raw material liquid by utilizing an osmotic gas synovial membrane component, and then filtering metal ions or particles by strong acid styrene cation exchange resin or weak acid acrylic cation exchange resin; the disclosures of CN102190611 and CN102001986A show that resin treatment and filtration are performed, but the resin needs regeneration and material replacement, so that industrial sewage treatment and material waste are large, the metal ion content in the product is trace impurities, and the regeneration liquid such as hydrochloric acid used in the resin regeneration link needs high-purity reagents, so that it is difficult to ensure the metal impurity content, which indirectly increases the production and environmental treatment cost, and is not suitable for industrial production and purification. However, in general, the above methods are complex in operation process, difficult in operation control, large in energy consumption and low in efficiency, and at present, the purity of domestic N-methyl pyrrolidone is between 99.5% and 99.9%, the content of metal ions is basically between 20 ppb and 30ppb, and the national standard does not provide a requirement for controlling the particle size of N-methyl pyrrolidone, but domestic semiconductor enterprises generally require that the content of metal ions in N-methyl pyrrolidone is 0.1ppb, and the particle content is 5 particles/ml (0.5um), so how to provide a method for producing N-methyl pyrrolidone with simple operation process and high purity is a problem that needs to be solved urgently by technical staff in the field.
Disclosure of Invention
The invention aims to provide a method for purifying semiconductor grade N-methyl pyrrolidone, which aims to solve the problems of complicated preparation process and difficult process control in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme: a purification method of semiconductor grade N-methyl pyrrolidone comprises the following steps;
s1: introducing methylamine gas into industrial grade N-methylpyrazine, reacting for 0.5-1.5 hours at 20-40 ℃, adsorbing and dehydrating through a 4A molecular sieve at the flow rate of 5-7L/min,
s2: performing membrane filtration twice on the obtained pretreatment liquid by adopting a composite membrane with the aperture of 0.1-0.2 um, performing reduced pressure rectification on the obtained filtrate under 20-85 KPa,
s3: collecting 80-120 deg.C fraction from the top of the rectifying tower, condensing, passing through an ion exchange device composed of strong acid cation exchange resin column and strong base anion exchange resin column in series,
s4: removing amine, cation and anion impurities in the N-methylpyrrolidone through ion exchange, and finally performing three-stage membrane filtration through a microporous membrane to obtain the target product.
2. The production method according to claim 1, wherein the mass ratio of methylamine to industrial grade N-methylpyrrolidone is 2-8: 1.
Preferably, the mass ratio of the methylamine to the industrial grade N-methyl pyrrolidone is 3-7: 1.
Preferably, the light fraction is discharged at a flow rate of 3-5L/min from a light fraction discharge port at the rectifying tower 2/3.
Preferably, the temperature of the dehydration process is controlled to be 20-40 ℃.
Preferably, the composite membrane adopted by twice membrane filtration of the pretreatment solution is a complexing agent composite membrane.
Preferably, the pretreatment solution is subjected to membrane filtration twice, wherein a beta-cyclodextrin composite membrane is adopted for the first membrane filtration, and an 18-crown 6 composite membrane is adopted for the second membrane filtration.
Preferably, the condensed water passes through an ion exchange device consisting of a strong acid cation exchange resin column and a strong base anion exchange resin column which are connected in series.
Preferably, the strong acid cation exchange resin column and the strong base anion exchange resin column are pretreated before use.
Preferably, the pretreatment step is as follows:
1) after the cation exchange resin is transformed into H type, the cation exchange resin is washed by high-purity water until the conductivity of the resin washing water is 1-10 pS/cm;
2) and (3) converting the anion exchange resin into an H type, and then cleaning the anion exchange resin with high-purity water until the conductivity of the resin cleaning effluent is 1-10 uS/cm.
11. The method of claim 1, wherein the resin is passed through a microfiltration membrane having a pore size of 0.01 to 1.0 μm.
Preferably, the reactor contacting with the material in each process of preparing the ultrapure N-methyl pyrrolidone and the material transmission pipeline between processes of each process are both made of high-purity quartz; the product storage tanks used are all storage tanks made of high-purity perfluorinated materials.
Compared with the prior art, the invention has the beneficial effects that: the N-methylpyrrolidine is pretreated, so that Y-butyrolactone impurities doped in the raw materials can be effectively removed, the problems of unstable product quality, high production cost and the like are solved, and the method adopts the cyclodextrin composite membrane and the 18-crown-6 composite membrane for membrane filtration, can effectively remove impurity metal ions, is simple and convenient to operate, has a good effect, and is suitable for industrial continuous production.
Drawings
FIG. 1 is a process flow diagram of the production method of the present invention.
In the figure: 1. a high purity quartz reactor; 2. a filter; 3. 4A molecular sieve adsorber; 4. a primary membrane filter; 5. a secondary membrane filter; 6. a rectifying tower; 7. a cation exchange resin tree; 8. an anion exchange resin; 9. a tertiary membrane filter; 10. and (5) a finished product groove.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the present invention provides a technical solution: a method for purifying semiconductor grade N-methyl pyrrolidone,
example 1
Preparation of N-methylpyrrolidone pretreatment solution:
350kg of industrial grade N-methyl alkyl chloride is added into a 500L pure quartz reactor 1 with a heating device, a stirring device, a thermometer and a gas distributor, the temperature is controlled at 30 +/-5 ℃, methylamine gas is continuously introduced into the industrial grade N-methyl alkyl chloride through the gas distributor at the flow rate of 5L/min under the stirring condition (the feeding ratio of the methylamine gas to the industrial grade NP is 4:1, the mass ratio) and the temperature is maintained for reaction for 1 hour; and (3) introducing the obtained N-methylpyrrolidone into a filter 2 for filtering, and then dehydrating through a 4A molecular sieve adsorber 3 of 400X600m at the temperature of 30-40 ℃ and at the flow rate of 6L/min to obtain an N-methylpyrrolidone pretreatment solution.
Preparing an N-methylpyrrolidone ion exchange device:
1) after the cation exchange resin is transformed into H type, the cation exchange resin is washed by high-purity water until the conductivity of the resin washing water is 1-10 pS/cm;
2) and (3) converting the anion exchange resin into an H type, and then cleaning the anion exchange resin with high-purity water until the conductivity of the resin cleaning effluent is 1-10 uS/cm.
Respectively loading the pretreated resins into a container
The ion exchange columns are connected in series to form the ion exchange device containing the strong-acid cation exchange resin column and the strong-base anion exchange resin column.
Sequentially introducing the N-methylpyrrolidone pretreatment solution into a primary membrane filter 4 and a secondary membrane filter 5 under the pressure of 0.5MPa, and performing primary membrane filtration through a beta-cyclodextrin composite membrane with the pore diameter of 0.1 mu m and secondary membrane filtration through an 18-crown-6 composite membrane with the pore diameter of 0.1 mu m to remove impurity metal ions and solid particles. The obtained filtrate is pressed into a rectifying tower 6 (tower kettle 500L, tower diameter 300mm and tower height 5000m), and is rectified under the conditions of 80KPa and tower top temperature of 120 ℃. In the rectification process, collecting light fractions at a light fraction discharge port at a rectification tower 2/3 at a flow rate of 3-5L/min, and storing the light fractions in a collecting tank 8 (for recycling); NMP fraction collected from the top of the rectifying tower is condensed and stored in a product fraction collecting tank 7, and is conveyed to a resin filter 9 through a high-purity quartz pipeline, and three-stage membrane filtration of 0.01-1 mu m is carried out under the pressure of 0.5MPa, so that an ultra-pure N-methyl pyrrolidone product is obtained and is stored in a high-purity perfluoro storage tank 10.
Detecting the purity of the product, wherein the chromaticity is analyzed by a visual colorimetry by taking platinum diamond standard liquid as a standard color;
the content is analyzed by gas chromatography; the water content is analyzed by Karl Fischer method, the evaporation residue is analyzed by gravimetric method; analyzing the positive ions by adopting a plasma mass spectrometry (ICP-MS); the anion was analyzed by ion exchange chromatography.
Name and model of test instrument
See table 1 for purity test results
Example 2
Preparation of N-methyl pyrrolidone pretreatment liquid
Adding 350kg of industrial grade N-methyl pyrrolidone into a pure quartz reactor with a heating device, a stirring device, a thermometer and a gas distributor, controlling the temperature at 35 ℃ and 5 ℃, continuously introducing methylamine gas into the industrial grade N-methyl pyrrolidone at the flow rate of 6L/min through the gas distributor under the stirring condition (the feeding ratio of the methylamine gas to the industrial grade NP is 6:1, the mass ratio) and maintaining the temperature for reacting for 1.5 hours; and then dehydrating the mixture by a 4A molecular sieve adsorber of 400 multiplied by 600m at the temperature of 20-30 ℃ and at the flow rate of 6L/min, and filtering the dehydrated mixture to obtain the N-methylpyrrolidine pretreatment solution.
The production method of the N-methyl pyrrolidone comprises the following steps:
performing first membrane filtration on the N-methylpyrrolidone pretreatment solution through a beta cyclodextrin composite membrane with the aperture of 0.2pm under the pressure of 0.5MPa, and performing second membrane filtration through an 18-crown-6 composite membrane with the aperture of 0.2m under the same pressure; pressing the filtrate into a rectifying tower (tower kettle 500L, tower diameter 300mm and tower height 5000mm), rectifying at 40KPa and tower top temperature 80 ℃, collecting light fraction (recycling) at a light fraction discharge port at 2/3 of the rectifying tower at a flow rate of 3-6L/min in the rectifying process, condensing NMP fraction collected from the top of the rectifying tower, filtering by a resin filter 9 at a pressure of 0.01-1 mu m through a three-stage membrane at a pressure of 0.5MPa to obtain an ultra-pure N-methyl pyrrolidone product, and storing in a high-purity perfluoro storage tank 10.
Obtaining a target product, and analyzing and detecting the purity of the target product.
The purity of the product was measured according to the method of example 1, and the results are shown in Table 1.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. Furthermore, it should be understood that although the present specification describes embodiments, this does not include only one embodiment, and such description is for clarity only, and those skilled in the art should be able to make the specification as a whole, and the embodiments may be appropriately combined to form other embodiments understood by those skilled in the art.
TABLE 1
Claims (12)
1. A method for purifying semiconductor grade N-methyl pyrrolidone is characterized by comprising the following steps;
s1: introducing methylamine gas into industrial grade N-methylpyrazine, reacting for 0.5-1.5 hours at 20-40 ℃, adsorbing and dehydrating through a 4A molecular sieve at the flow rate of 5-7L/min,
s2: performing membrane filtration twice on the obtained pretreatment liquid by adopting a composite membrane with the aperture of 0.1-0.2 um, performing reduced pressure rectification on the obtained filtrate under 20-85 KPa,
s3: collecting 80-120 deg.C fraction from the top of the rectifying tower, condensing, passing through an ion exchange device composed of strong acid cation exchange resin column and strong base anion exchange resin column in series,
s4: removing amine, cation and anion impurities in the N-methylpyrrolidone through ion exchange, and finally performing three-stage membrane filtration through a microporous membrane to obtain the target product.
2. The production method according to claim 1, wherein the mass ratio of methylamine to industrial grade N-methylpyrrolidone is 2-8: 1.
3. The production method according to claim 2, wherein the mass ratio of methylamine to industrial grade N-methylpyrrolidone is 3-7: 1.
4. The method as claimed in claim 1, wherein the light fraction is discharged at a flow rate of 3 to 5L/min from a light fraction discharge port at the rectifying tower 2/3.
5. The method according to claim 1, wherein the temperature of the dehydration process is controlled to be 20-40 ℃.
6. The method of claim 1, wherein the composite membrane used for the twice membrane filtration of the pretreatment solution is a complexing agent composite membrane.
7. The method of claim 6, wherein the pretreatment solution is subjected to two membrane filtrations, wherein the first membrane filtration is performed by using a beta-cyclodextrin composite membrane, and the second membrane filtration is performed by using an 18-crown 6 composite membrane.
8. The method of claim 1, wherein the condensed product is passed through an ion exchange unit comprising a strong acid cation exchange resin column and a strong base anion exchange resin column in series.
9. The method of claim 1, wherein the strong acid cation exchange resin column and the strong base anion exchange resin column are pre-treated before use.
10. The method of claim 1, wherein the pre-treating step comprises:
1) after the cation exchange resin is transformed into H type, the cation exchange resin is washed by high-purity water until the conductivity of the resin washing water is 1-10 pS/cm;
2) and (3) converting the anion exchange resin into an H type, and then cleaning the anion exchange resin with high-purity water until the conductivity of the resin cleaning effluent is 1-10 uS/cm.
11. The method of claim 1, wherein the resin is passed through a microfiltration membrane having a pore size of 0.01 to 1.0 μm.
12. The method of claim 1, wherein the reactor in contact with the material in each process and the material conveying pipeline between processes in each process for preparing the ultrapure N-methyl pyrrolidone are made of high-purity quartz; the product storage tanks used are all storage tanks made of high-purity perfluorinated materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110760811.1A CN113429329A (en) | 2021-07-06 | 2021-07-06 | Purification method of semiconductor grade N-methyl pyrrolidone |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181130A (en) * | 2021-12-16 | 2022-03-15 | 浙江联盛化学股份有限公司 | Purification method of N-methyl pyrrolidone |
| CN115160225A (en) * | 2022-09-01 | 2022-10-11 | 阜新泽程化工有限责任公司 | Industrial production method of electronic pure pyrazole |
| CN116239514A (en) * | 2023-03-20 | 2023-06-09 | 重庆中润新材料股份有限公司 | Method for reducing free amine in NMP |
| EP4201922A1 (en) * | 2021-12-22 | 2023-06-28 | Jaewon Industrial Co., Ltd | Method for purifying wasted solution comprising n-methyl-2-pyrrolidone |
| CN117398707A (en) * | 2023-09-07 | 2024-01-16 | 湖北兴福电子材料股份有限公司 | Electronic grade hexamethyldisilazane purification device and purification method |
| US20240039069A1 (en) * | 2021-06-22 | 2024-02-01 | Guangdong Brunp Recycling Technology Co., Ltd. | Method for treating scrapped positive electrode slurry, and application |
| CN117624010A (en) * | 2023-11-27 | 2024-03-01 | 重庆中润新材料股份有限公司 | Pretreatment method for recycling NMP |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20240039069A1 (en) * | 2021-06-22 | 2024-02-01 | Guangdong Brunp Recycling Technology Co., Ltd. | Method for treating scrapped positive electrode slurry, and application |
| CN114181130A (en) * | 2021-12-16 | 2022-03-15 | 浙江联盛化学股份有限公司 | Purification method of N-methyl pyrrolidone |
| EP4201922A1 (en) * | 2021-12-22 | 2023-06-28 | Jaewon Industrial Co., Ltd | Method for purifying wasted solution comprising n-methyl-2-pyrrolidone |
| CN115160225A (en) * | 2022-09-01 | 2022-10-11 | 阜新泽程化工有限责任公司 | Industrial production method of electronic pure pyrazole |
| CN116239514A (en) * | 2023-03-20 | 2023-06-09 | 重庆中润新材料股份有限公司 | Method for reducing free amine in NMP |
| CN116239514B (en) * | 2023-03-20 | 2023-11-10 | 重庆中润新材料股份有限公司 | Method for reducing free amine in NMP |
| CN117398707A (en) * | 2023-09-07 | 2024-01-16 | 湖北兴福电子材料股份有限公司 | Electronic grade hexamethyldisilazane purification device and purification method |
| CN117624010A (en) * | 2023-11-27 | 2024-03-01 | 重庆中润新材料股份有限公司 | Pretreatment method for recycling NMP |
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