CN110407729A - A method of preventing the discoloration deterioration of N methyl pyrrolidone - Google Patents
A method of preventing the discoloration deterioration of N methyl pyrrolidone Download PDFInfo
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- CN110407729A CN110407729A CN201910776146.8A CN201910776146A CN110407729A CN 110407729 A CN110407729 A CN 110407729A CN 201910776146 A CN201910776146 A CN 201910776146A CN 110407729 A CN110407729 A CN 110407729A
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- tower
- negative pressure
- nmp
- methyl pyrrolidone
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Detergent Compositions (AREA)
Abstract
A method of preventing the discoloration deterioration of N methyl pyrrolidone, it is poly- including pretreatment, three-tower rectification step: where pretreatment is to add alkali in NMP material liquid to be processed and be sufficiently stirred, and pH value is between 10~11 after adjusting, it is then injected into head tank, turns rectification process；Three-tower rectification is taken in rectifying, and No.1 tower reactor is atmospheric tower or negative pressure tower, controls bottom temperature, and the temperature in tower reactor is less than or equal to 180 DEG C, and tower top temperature is less than or equal to 100 DEG C, and function is dehydration and part light components；No. two tower reactors are negative pressure tower, and function is dehydration and lightweight component, and No. three tower reactors are negative pressure tower, and function is removing heavy component, obtain finished product；The substance that show color in the NMP product that recycling obtains can be thoroughly removed using the present invention, improved NMP product purity, made finished product purity >=99.9% of NMP product, quality is more stable, there is no metachromatism, the phase that preserves value improves 7 times or more than existing finished product, reduces purification number.
Description
Technical field:
The present invention relates to the processing methods for preventing N methyl pyrrolidone (abbreviation NMP) discoloration deterioration.
Background technique:
N-Methyl pyrrolidone, Chinese nickname: NMP；- 2 pyrrolidones of 1- methyl；N-methyl-2-pyrrolidone.It is colourless
Bright oily liquids, micro- smell for having amine.Volatility is low, and thermal stability, chemical stability are good, can volatilize with vapor.There is suction
It is moist.It is light sensitive.Soluble easily in water, ethyl alcohol, ether, acetone, ethyl acetate, chloroform and benzene can dissolve most of organic and nothing
Machine compound, polar gas, natural and synthetic macromolecular compound.N-Methyl pyrrolidone lithium electricity, medicine, pesticide, pigment,
It is widely applied in the industries such as cleaning agent, insulating materials.
Spent anolyte can be generated in Production Process of Lithium Battery, and in spent anolyte (referred to as containing N methyl pyrrolidone
NMP), since NMP is expensive, people try NMP in the anode waste material to lithium battery and are recycled, in returning for NMP
It during midwifery produces, is easy to change colour during storage it is found by the applicant that recycling resulting NMP, recycles resulting NMP storage
After three months, product colour turns yellow, and as time went on, the quantity of jaundice increases, and darkens.It seeks advice from according to investigations, NMP's
Generally existing such problems in industry is recycled, and above-mentioned phenomenon is then not present in the finished product of commercial synthesis.
Conscientious detection and analysis is carried out for above-mentioned phenomenon applicant, it is found by the applicant that: exist in the NMP liquid of recycling
Such a substance, this substance can play chromogenic reaction with alkali, meet alkali pinkiness or aubergine, it is that colourless NMP liquid becomes
The main cause of color, recycling after resulting colourless NMP liquid meets alkali will become pink or aubergine, and the resting period is too long, becomes
Yellow, this substance can not detect under common gas spectral condition.
Through applicant's repetition test, NMP liquid can generate this substance that show color under excessively high rectification temperature, especially in tower
When liquid is evaporated fastly in kettle, temperature is excessively high, and the possibility for generating this substance that show color is high.
Substance that show color rectifying under the conditions of different alkali numbers has presence, the early period of rectifying or later period all there may be,
As the time gradually decreases if if early period, pink is more and more lighter, finally disappears, this is related with caustic dosage；If rear
Gradually become more as temperature is got higher if phase, main cause may be basicity mistake after excessively high bottom temperature or liquid concentration
Height illustrates that this substance can be taken out of with NMP azeotropic by NMP, can regenerate again under the high temperature conditions.
Since the nmp solution of recycling contains this substance, this substance may be at salt after encountering alkali, or disappears and turn
Become another substance, so the NMP of recycling can change colour after meeting alkali.
Summary of the invention:
The N methyl pyrrolidone discoloration deterioration recycled in order to prevent, the present invention provides one kind to prevent N methyl pyrrolidone
Change colour the method deteriorated.
The technical solution adopted by the present invention is as follows:
A method of the discoloration deterioration of N methyl pyrrolidone is prevented, it is characterized in that: including that following step is poly-:
Poly- one is walked, pretreatment:
Add alkali in NMP material liquid to be processed and be sufficiently stirred, pH value is then injected into original between 10~11 after adjusting
In batch can, turn rectification process；
Poly- two are walked, rectifying:
Three-tower rectification is taken, No.1 tower reactor is atmospheric tower or negative pressure tower, controls bottom temperature, and the temperature in tower reactor is less than etc.
In 180 DEG C, tower top temperature is less than or equal to 100 DEG C, and function is a large amount of water of removing and part light components；No. two tower reactors are negative pressure
Tower, function are to remove remaining water and remaining lightweight component, and No. three tower reactors are also negative pressure tower, and function is removing heavy group
Point, obtain finished product；
Poly- three are walked, packs and stores:
Packaging and storage are carried out according to arm's length standard, are kept in dark place, and are stored at shady and cool ventilation drying.
Further, in step 2, No.1 tower reactor is negative pressure tower.
Further, in step 2, the negative pressure value in No. two tower reactors is 0.5~1.0, and negative pressure value is 0.5 in No. three tower reactors
~1.0.
Further, the negative pressure value in No.1 tower reactor is 0.5~1.0.
Further, in step 2, the temperature in No.1 tower reactor is 90 DEG C~150 DEG C, and tower top temperature is 80 DEG C~100
℃。
Further, in step 2, the temperature in No.1 tower reactor is 85 DEG C~120 DEG C, and tower top temperature is 80 DEG C~90
℃。
Beneficial effects of the present invention:
The substance that show color in the NMP product that recycling obtains can be thoroughly removed using the present invention, improve NMP product purity,
Make finished product purity >=99.9% of NMP product, quality is more stable, and metachromatism is not present, and the value preserving phase improves 7 times than existing finished product
More than, purification number is reduced, 1% NMP product is greater than for impurity content, then can just final product quality be made to reach by secondary rectifying
To 99.9% or more.
Specific embodiment:
A method of the discoloration deterioration of N methyl pyrrolidone is prevented, including is walked as follows poly-:
Poly- one is walked, pretreatment:
Add alkali in NMP material liquid to be processed and be sufficiently stirred, pH value is then injected into original between 10~11 after adjusting
In batch can, rectification process is waited；
In this example, in 30% liquid that (mass fraction) between 0.05%-0.1% is added in NMP material liquid to be processed
Alkali), for pH value 10.5 or so, 1 hour left side is sufficiently stirred depending on raw material condition in specific addition after making NMP waste liquid that alkali be added to adjust
Then the right side will add the raw material after alkali to squeeze into head tank, wait next step rectification process.
Poly- two are walked, rectifying:
Three-tower rectification is taken, No.1 tower reactor is atmospheric tower, controls bottom temperature, and the temperature in tower reactor is less than or equal to 180 DEG C,
Tower top temperature is less than or equal to 100 DEG C, and function is a large amount of water of removing and part light components；No. two tower reactors are negative pressure tower, function
Can remove remaining water and remaining light components, No. three tower reactors are negative pressure tower, and function is removing heavy constituent, obtain finished product；
In this column, the negative pressure value in No. two tower reactors is 0.5~1.0, and negative pressure value is 0.5~1.0 in No. three tower reactors；
Temperature in No.1 tower reactor is 90 DEG C~150 DEG C, and tower top temperature is 80 DEG C~90 DEG C；
Poly- three are walked, packs and stores:
Packaging and storage are carried out according to arm's length standard, are kept in dark place, and are stored at shady and cool ventilation drying；
By adding alkali that can remove NMP material liquid, routinely rectifying and multiple rectifying are also difficult to the discoloration impurity removed, so that
Final product quality is more stable, it is easier to save, be not in discoloration within the shelf-life, the NMP material liquid of existing recycling is avoided to make
Used time needs secondary rectifying, and it is artificial to reduce energy consumption, reduces rectifying cost, reduces the production difficulty of microelectronics grade NMP.
Rectifying, control are carried out by existing rectifying production procedure and state modulator to rectifying nmp solution to pretreated
Rectifying tower reactor temperature be lower than 180 DEG C, to nmp solution carry out distillation process in alkali is added, after adjusting pH value between 10~11,
So that some in nmp solution be difficult to isolated organic matter and removed by way of chemical reaction, to reduce the difficulty of the purification of NMP
Degree, needs to prevent Organic Sodium Salt from constantly accumulating kettle residual continued emissions during steady production, blocks pipeline, especially miscellaneous
The higher raw material of matter.
In the present embodiment, rectifying column used in rectification process is manufactured and designed by good fortune in Tianjin, and the main of No.1 tower reactor is appointed
Business is to be dehydrated and remove lightweight component in part therein；The task of No. two tower reactors is removing light components and dehydration, No. three tower reactors
Task be that removing and generates finished product at heavy component, in distillation process plus alkali (sodium hydroxide), by way of chemical reaction
It can remove and be difficult to isolated discoloration impurity in nmp solution, then the finished product of higher purity can be obtained by rectifying mode.
A specific embodiment of the invention is exemplified below:
There are many embodiments of the present invention, and the technical thought of embodiment according to the present invention is enlightenment, said by above-mentioned
Bright content, relevant staff completely can without departing from the scope of the technological thought of the present invention', carry out multiplicity change with
And modification.The technical scope of the present invention is not limited to the contents of the specification, it is necessary to according to scope of the claims come
Determine its technical scope.
Claims (6)
1. a kind of method for preventing the discoloration deterioration of N methyl pyrrolidone, it is characterized in that: including that following step is poly-:
Poly- one is walked, pretreatment:
Add alkali in NMP material liquid to be processed and be sufficiently stirred, pH value is then injected into head tank between 10~11 after adjusting
In, turn rectification process；
Poly- two are walked, rectifying:
Three-tower rectification is taken, No.1 tower reactor is atmospheric tower or negative pressure tower, controls bottom temperature, the temperature in tower reactor is less than or equal to
180 DEG C, tower top temperature is less than or equal to 100 DEG C, and function is a large amount of water of removing and part light components；No. two tower reactors are negative pressure
Tower, function are to remove remaining water and remaining lightweight component, and No. three tower reactors are also negative pressure tower, and function is removing heavy group
Point, obtain finished product；
Poly- three are walked, packs and stores:
Packaging and storage are carried out according to arm's length standard, are kept in dark place, and are stored at shady and cool ventilation drying.
2. the method for preventing the discoloration deterioration of N methyl pyrrolidone according to claim 1, it is characterized in that: in step 2, one
Number tower reactor is negative pressure tower.
3. the method for preventing the discoloration deterioration of N methyl pyrrolidone according to claim 1, it is characterized in that: in step 2, two
Negative pressure value in number tower reactor is 0.5~1.0, and negative pressure value is 0.5~1.0 in No. three tower reactors.
4. the method for preventing the discoloration deterioration of N methyl pyrrolidone according to claim 2, it is characterized in that: in No.1 tower reactor
Negative pressure value is 0.5~1.0.
5. the method for preventing the discoloration deterioration of N methyl pyrrolidone according to claim 1, it is characterized in that: in step 2, one
Temperature in number tower reactor is 90 DEG C~150 DEG C, and tower top temperature is 80 DEG C~100 DEG C.
6. the method for preventing the discoloration deterioration of N methyl pyrrolidone according to claim 4, it is characterized in that: in step 2, one
Temperature in number tower reactor is 85 DEG C~120 DEG C, and tower top temperature is 80 DEG C~90 DEG C.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910776146.8A CN110407729A (en) | 2019-08-22 | 2019-08-22 | A method of preventing the discoloration deterioration of N methyl pyrrolidone |
| CN202010712424.6A CN111675642A (en) | 2019-08-22 | 2020-07-22 | Method for preventing discoloration and deterioration of N-methyl pyrrolidone and product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910776146.8A CN110407729A (en) | 2019-08-22 | 2019-08-22 | A method of preventing the discoloration deterioration of N methyl pyrrolidone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110407729A true CN110407729A (en) | 2019-11-05 |
Family
ID=68368429
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910776146.8A Pending CN110407729A (en) | 2019-08-22 | 2019-08-22 | A method of preventing the discoloration deterioration of N methyl pyrrolidone |
| CN202010712424.6A Withdrawn CN111675642A (en) | 2019-08-22 | 2020-07-22 | Method for preventing discoloration and deterioration of N-methyl pyrrolidone and product thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010712424.6A Withdrawn CN111675642A (en) | 2019-08-22 | 2020-07-22 | Method for preventing discoloration and deterioration of N-methyl pyrrolidone and product thereof |
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| Country | Link |
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| CN (2) | CN110407729A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114452669A (en) * | 2022-03-30 | 2022-05-10 | 派尔森环保科技有限公司 | NMP-containing feed liquid recycling, rectifying and purifying system |
| CN115477603A (en) * | 2021-11-12 | 2022-12-16 | 金为环保科技(常州)有限公司 | Method for improving stability of recovered NMP and product thereof |
| CN115636777A (en) * | 2022-09-05 | 2023-01-24 | 九江紫昊新材料有限公司 | N-methyl pyrrolidone energy-saving recovery process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4965370A (en) * | 1989-08-21 | 1990-10-23 | Phillips Friedman Company | N-methyl-2-pyrrolidone purification |
| JPH0314559A (en) * | 1989-06-12 | 1991-01-23 | Dainippon Ink & Chem Inc | Method for reducing impurity in n-methyl-2-pyrrolidone |
| CN104797558A (en) * | 2012-11-22 | 2015-07-22 | 巴斯夫欧洲公司 | Method for purifying N-alkylpyrrolidones |
| CN108654130A (en) * | 2018-07-17 | 2018-10-16 | 天津中福环保科技股份有限公司 | The method and apparatus of NMP recycling heat pump distillation in a kind of production of lithium electricity |
-
2019
- 2019-08-22 CN CN201910776146.8A patent/CN110407729A/en active Pending
-
2020
- 2020-07-22 CN CN202010712424.6A patent/CN111675642A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0314559A (en) * | 1989-06-12 | 1991-01-23 | Dainippon Ink & Chem Inc | Method for reducing impurity in n-methyl-2-pyrrolidone |
| US4965370A (en) * | 1989-08-21 | 1990-10-23 | Phillips Friedman Company | N-methyl-2-pyrrolidone purification |
| CN104797558A (en) * | 2012-11-22 | 2015-07-22 | 巴斯夫欧洲公司 | Method for purifying N-alkylpyrrolidones |
| CN108654130A (en) * | 2018-07-17 | 2018-10-16 | 天津中福环保科技股份有限公司 | The method and apparatus of NMP recycling heat pump distillation in a kind of production of lithium electricity |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115477603A (en) * | 2021-11-12 | 2022-12-16 | 金为环保科技(常州)有限公司 | Method for improving stability of recovered NMP and product thereof |
| CN114452669A (en) * | 2022-03-30 | 2022-05-10 | 派尔森环保科技有限公司 | NMP-containing feed liquid recycling, rectifying and purifying system |
| CN115636777A (en) * | 2022-09-05 | 2023-01-24 | 九江紫昊新材料有限公司 | N-methyl pyrrolidone energy-saving recovery process |
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| Publication number | Publication date |
|---|---|
| CN111675642A (en) | 2020-09-18 |
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Application publication date: 20191105 |