CN108794371A - A kind of process for purification of N-Methyl pyrrolidone product - Google Patents
A kind of process for purification of N-Methyl pyrrolidone product Download PDFInfo
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- CN108794371A CN108794371A CN201710287359.5A CN201710287359A CN108794371A CN 108794371 A CN108794371 A CN 108794371A CN 201710287359 A CN201710287359 A CN 201710287359A CN 108794371 A CN108794371 A CN 108794371A
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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
Abstract
The invention discloses a kind of process for purification of N-Methyl pyrrolidone product, in N-Methyl pyrrolidone product rectifier, one fractional condensaion system is set, the fractional condensaion system includes the heat exchanger of two or more controllable temperatures and corresponding return tank, specifically includes following steps：The N-Methyl pyrrolidone for needing purification is sent into rectifying column and is distilled, the overhead of rectifying column carries out level-one condensation, it is sent into secondary heat exchanger condensation through the condensed gas-phase product of level-one, the condensed liquid product of level-one is sent into level-one return tank, gas-phase product discharge after B-grade condensation, liquid product after B-grade condensation is back to rectifying column, and the product section in level-one return tank is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product.Present invention investment is small, low energy consumption, easily operated, simply and efficiently removes unhindered amina and light miscellaneous, obtains the N-Methyl pyrrolidone product of high-quality.
Description
Technical field
The invention belongs to chemical technology fields, and in particular to a kind of process for purification of N-Methyl pyrrolidone product.
Background technology
Pyrrolidones is a kind of product category being widely used in the industries such as solvent, chemical industry, medicine, includes N- methyl pyrroles
Pyrrolidone（NMP）, N- ethyl pyrrolidones（NEP）It is that the polarity that selectivity is strong, stability is good is molten Deng, wherein NMP and NEP
Agent has many advantages, such as that moderate boiling point, high-flash, hypotoxicity and solvability are strong；NMP can be used for the extractants such as butadiene, aromatic hydrocarbons,
The purifying of acetylene, alkene, alkadienes, many engineering plastics（Polyvinylidene fluoride etc.）Solvent, the electrode of lithium ion battery is auxiliary
Material, photoresist is helped to remove liquid, the production of LCD liquid crystal materials, the cleaning etc. of semicon industry wiring board；NEP can be used for medicine, height
The industries such as shelves solvent.
By taking N-Methyl pyrrolidone as an example, existing pyrrolidones preparation method is：Using gamma-butyrolacton and methylamine（40%）
With 1：1.10 ~ 1.20 molar ratio carries out thermal condensation reaction, then concentrated and vacuum distillation can obtain purity>99% finished product.
Currently, N-Methyl pyrrolidone is broadly divided into regular grade, technical grade, electron level, SILVER REAGENT, purity is required to reach respectively
To 99.5%, 99.8%, 99.9%, 99.9%, wherein electron level and SILVER REAGENT also requires methylamine content≤5ppm, moisture in product to contain
≤ 0.02%, pH is measured between 7-9, coloration≤10.It is original to use gamma-butyrolacton and monomethylamine aqueous solution in existing production technology
Material synthesis N-Methyl pyrrolidone, for distillation process, the general water using in the remaining methylamine of first elimination reaction and crude product,
Finished N-methyl pyrrolidones is obtained in product rectifying column again, the production procedure as disclosed in CN 200910064504.By this
Technology can realize 99.9% N-Methyl pyrrolidone product purity, but the quality of the N-Methyl pyrrolidone after purifying still reaches
Less than the requirement of SEMI C12, one of problem be the alkaline impurities contents such as unhindered amina such as methylamine be difficult to decrease 5ppm with
Under；Light miscellaneous such as tetrahydrofuran, formamide are as the light miscellaneous use that may be caused in downstream application in electronics, medicine simultaneously
There is potential deviation.Therefore the method for purification for developing new N-Methyl pyrrolidone product, the N- methylpyrroles after making it purify
Alkanone purity and its impurity content（Such as methylamine content）It disclosure satisfy that the requirement of SEMI C12 is extremely urgent.
The removing of free amine mainly uses ion exchange resin and acid fiber to adsorb in existing N-Methyl pyrrolidone
The method of removing purifies N- first as Chinese patent application CN102001986A and CN102190611A are disclosed with ion-exchange
The method of base pyrrolidones；Acid ion exchange fiber disclosed in Chinese patent application CN201310019294.8 proposes N- first
The method of base pyrrolidones.Patent CN102001986A need to be used by macroporous absorbent resin, strong-acid ion exchange resin, highly basic
Property ion exchange resin composition ion interchange unit；Patent CN102190611A need to be used by non-polar macroporous resin column and band
The ion interchange unit of electric cellulose membrane composition, the amberlite lipid species that the methods of this two patent application publications uses
It is more, complicated for operation, and treatment effeciency is relatively low, or need to increase organic alcohols, it causes to N-Methyl pyrrolidone product
Secondary pollution.Patent CN201310019294.8 discloses the method adsorbed using ion-exchange fibre and take off unhindered amina, exists fine
It is relatively low to tie up adsorption efficiency, early period product moisture and coloration content it is high, and the defects of need using strong acid, therefore, it is difficult in industry
In economically implemented.
For optimize technique working condition, production cost is reduced to greatest extent, realizes carrying for N-Methyl pyrrolidone product
Sublimate produces high-quality N-Methyl pyrrolidone product, how to select specific technological process and equipment very crucial.
Invention content
The purpose of the present invention is to provide a kind of process for purification of N-Methyl pyrrolidone product, pass through the control that condenses and flow back
System, obtains the N-Methyl pyrrolidone product of high-quality.
To achieve the goals above, the technical solution adopted by the present invention is：
A fractional condensaion system is arranged in a kind of N-Methyl pyrrolidone process for purification, N-Methyl pyrrolidone product rectifier
System, the fractional condensaion system includes the heat exchanger of two or more controllable temperatures and corresponding return tank.
Preferably, the fractional condensaion system includes first order heat exchanger and second level heat exchanger, and first order heat exchanger connects
It is connected to level-one return tank；The rectifying column tower top distillate is condensed by first order heat exchanger, control outlet streams temperature be 50 ~
120 DEG C, the condensed liquid product of first order heat exchanger enters level-one return tank, all as finished product extraction or part conduct
Finished product extraction is partly refluxed to rectifying column；The condensed gas-phase product of first order heat exchanger is condensed by second level heat exchanger, control
It is room temperature ~ 50 DEG C, the condensed product infinite reflux of second level heat exchanger to rectifying column to make mouthful stream temperature；Wherein, the essence
It is 1 ~ 10kpa to evaporate the control of column overhead pressure（Absolute pressure）, the gas phase fraction of the first order heat exchanger is 0.50 ~ 0.02.
Preferably, first order heat exchanger gas phase fraction is 0.40 ~ 0.05.
Preferably, first order heat exchanger gas phase fraction is 0.30 ~ 0.08.
Preferably, the extraction of first order return tank and reflux ratio are 1:0~2.0.
Preferably, the extraction of first order return tank and reflux ratio are 1:0~1.0.
Preferably, the extraction of first order return tank and reflux ratio are 1:0~0.2.
Preferably, N-Methyl pyrrolidone has the characteristics that light miscellaneous and unhindered amina impurity is relatively low in the finished product, described
Light miscellaneous less than 0.05wt%, the unhindered amina total amount is less than 5ppm.
More specifically, when above-mentioned fractional condensaion system uses condensed in two stages, a kind of essence of N-Methyl pyrrolidone product
Method processed, that is, include the following steps：The N-Methyl pyrrolidone for needing purification is sent into rectifying column and is distilled, rectifying column
Overhead carries out level-one condensation, and the gas-phase product through level-one condensation carries out B-grade condensation, the condensed liquid product of level-one
It is sent into level-one return tank, the gas-phase product through B-grade condensation is discharged, and the liquid product after B-grade condensation is back to rectifying column, level-one
The product section in the extraction of product whole or level-one return tank in return tank is back to rectifying column, while part is used as N- first
Base pyrrolidones purified product produces.Rectifying tower pressure on top surface is 1 ~ 10 kPa；Level-one condensing condition：Temperature control is 50 ~ 120
DEG C, gas phase fraction be 2% ~ 50%, B-grade condensation condition：Temperature control is 20 ~ 50 DEG C.
Fractional condensaion parameter is one of vital parameter for light miscellaneous and unhindered amina removing, and the present inventor is by young
Thin experiment and theoretical examination find that unhindered amina such as monomethyl amine, formamide, dimethylamine etc. is that there are dissolubilities with NMP, or even are formed
A kind of intermolecular association power, so that boiling point difference is huge, but always present in product, but this
Dissolubility acts on higher temperature（50~120℃）It can be destroyed, so that the free amine content in NMP products declines to a great extent.
To realize currently, the present inventor passes through test of many times and theoretical calculation, the material outlet gas phase fraction of discovery first order heat exchanger
The important parameter for controlling this destruction dissolving, the unhindered amina total amount in NMP products and phase fraction of working off one's feeling vent one's spleen have it is inevitable contact,
And by experiment with caution, opereating specification of the present invention is obtained.
Wherein, gas phase fraction（Vapor Fraction）It is to refer to gas in gas-liquid two-phase fluid known to those skilled in the art
Mutually account for the percentage composition of total amount.Pressure and tower top/kettle temperature condition of NMP product towers is are well known in the art, as in vain
Heptan is pungent to write<1,4- butanediols, tetrahydrofuran and its derivative>, chapter 4 second saves detailed narration in Chemical Industry Press.
For the present invention, preferred rectifying tower pressure on top surface（Absolute pressure）For 1 ~ 10 kPa, tower top temperature is 95 ~ 128 DEG C, bottom of tower temperature
97 ~ 160 DEG C of degree.
The present invention is excessively high for unhindered amina impurity content in prior art N-Methyl pyrrolidone, cannot meet SEMI C12
Requirement and granular ion exchange resin and ion-exchange fibre efficiency it is low, technique and equipment are cumbersome, are not easy to regenerate, deposit
The N-Methyl pyrrolidone the defects of, a kind of support prior-art devices are provided and carry out technological transformation, you can are simply and efficiently gone
It except unhindered amina in N-Methyl pyrrolidone, and can further remove in N-Methyl pyrrolidone light miscellaneous, investment is small, low energy consumption, easily
In operation.Using condensed in two stages, reflux control in the present invention, most important for light miscellaneous and unhindered amina removing, unhindered amina is such as
Monomethyl amine, formamide, dimethylamine etc. are that there are dissolubilities with N-Methyl pyrrolidone, or even form a kind of intermolecular association
Active force, so that boiling point difference is huge, but always present in product, but this dissolubility acts on higher temperatures
Degree（50~120℃）It can be destroyed, so that the free amine content in N-Methyl pyrrolidone product declines to a great extent.Utilize this
Inventive technique scheme remove in N-Methyl pyrrolidone unhindered amina and it is light it is miscellaneous after, the purity, free of N-Methyl pyrrolidone can be made
Amine, volatile components and moisture technical indicator are considerably beyond electronics（SEMI C12）With the requirement of SILVER REAGENT.
Advantage of the invention is that only being reconfigured to existing equipment and process parameter control, additional energy is not increased
Amount, chemical material（Such as adsorbent, Organic Alcohol or sulfuric acid）, process is environmental clean, and the free amine content in finished product can
It realizes the regulation and control out of 0.1 ~ 5ppm, while further decreasing the light miscellaneous content of finished product, to improve product purity.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention.
Specific implementation mode
In order to keep the technical purpose, technical solution and advantageous effect of the present invention clearer, with reference to specific embodiment
Technical scheme of the present invention is further illustrated, but the embodiment is intended to explain the present invention, and should not be understood as pair
The limitation of the present invention, the person that is not specified actual conditions in embodiment carry out according to conventional conditions or manufacturer's recommended conditions.
Embodiment 1
A kind of process for purification of N-Methyl pyrrolidone product, includes the following steps：
As shown in Figure 1, it would be desirable to the N-Methyl pyrrolidone of purification（Raw material）It is sent into rectifying column 1 and distills, rectifying column 1
Overhead is sent into first-class heat exchanger 2 and carries out level-one condensation, and the gas-phase product through level-one condensation is sent into secondary heat exchanger 3 and is carried out
B-grade condensation, the condensed liquid product of level-one are sent into level-one return tank 4, the gas-phase product discharge through B-grade condensation, and two level is cold
Liquid product after solidifying is back to rectifying column 1 again through two level return tank 5, and the product section in level-one return tank 4 is back to rectifying
Tower 1, while part is produced as N-Methyl pyrrolidone purified product（Enter finished pot 6）；The bottom of tower of rectifying column 1 is connected with boils again
Device 7.
Wherein, 1 tower top pressure of rectifying column is 5.0 ~ 6.0kPa, and tower top temperature is 109.5 ~ 114.0 DEG C, column bottom temperature
110.0~117.0℃；The temperature control of first-class heat exchanger 2 is 105 ~ 109 DEG C, gas phase fraction is 10%, the temperature of secondary heat exchanger 3
Degree control is 30 ~ 32 DEG C, and the extraction of level-one return tank 4 and reflux ratio are 1：0.8.
Embodiment 2
A kind of process for purification of N-Methyl pyrrolidone product, includes the following steps：
It will need the N-Methyl pyrrolidone of purification（Raw material）Be sent into rectifying column and distill, the overhead of rectifying column into
Row level-one condenses, and the gas-phase product through level-one condensation carries out B-grade condensation, and the condensed liquid product of level-one is sent into level-one reflux
Tank, the gas-phase product discharge through B-grade condensation, liquid product after B-grade condensation are back to rectifying column again through two level return tank, and one
Product section in grade return tank is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product；Rectifying
The bottom of tower of tower is connected with reboiler.
Wherein, rectifying tower pressure on top surface is 3 ~ 4 kPa, and tower top temperature is 97 ~ 105 DEG C, 101 ~ 115 DEG C of column bottom temperature；One
Grade condensing condition：Temperature control is 95 ~ 98 DEG C, gas phase fraction is 15%, B-grade condensation condition：Temperature control be 28 ~ 30 DEG C, one
The extraction of grade return tank and reflux ratio are 1：0.4.
Embodiment 3
A kind of process for purification of N-Methyl pyrrolidone product, includes the following steps：
It will need the N-Methyl pyrrolidone of purification（Raw material）Be sent into rectifying column and distill, the overhead of rectifying column into
Row level-one condenses, and the gas-phase product through level-one condensation carries out B-grade condensation, and the condensed liquid product of level-one is sent into level-one reflux
Tank, the gas-phase product discharge through B-grade condensation, liquid product after B-grade condensation are back to rectifying column again through two level return tank, and one
Product section in grade return tank is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product；Rectifying
The bottom of tower of tower is connected with reboiler.
Wherein, rectifying tower pressure on top surface is 1 ~ 2 kPa, and tower top temperature is 74 ~ 83 DEG C, 79 ~ 90 DEG C of column bottom temperature；Level-one is cold
Solidifying condition：Temperature control is 50 ~ 51 DEG C, gas phase fraction is 2%, B-grade condensation condition：Temperature control is 20 ~ 22 DEG C, level-one reflux
The extraction of tank and reflux ratio are 1：0.1.
Embodiment 4
A kind of process for purification of N-Methyl pyrrolidone product, includes the following steps：
It will need the N-Methyl pyrrolidone of purification（Raw material）Be sent into rectifying column and distill, the overhead of rectifying column into
Row level-one condenses, and the gas-phase product through level-one condensation carries out B-grade condensation, and the condensed liquid product of level-one is sent into level-one reflux
Tank, the gas-phase product discharge through B-grade condensation, liquid product after B-grade condensation are back to rectifying column again through two level return tank, and one
Product section in grade return tank is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product；Rectifying
The bottom of tower of tower is connected with reboiler.
Wherein, rectifying tower pressure on top surface is 7 ~ 8 kPa, and tower top temperature is 117 ~ 122 DEG C, 120 ~ 130 DEG C of column bottom temperature；One
Grade condensing condition：Temperature control is 60 ~ 61 DEG C, gas phase fraction is 5%, B-grade condensation condition：Temperature control is 25 ~ 27 DEG C, level-one
The extraction of return tank and reflux ratio are 1：0.2.
Embodiment 5
A kind of process for purification of N-Methyl pyrrolidone product, includes the following steps：
It will need the N-Methyl pyrrolidone of purification（Raw material）Be sent into rectifying column and distill, the overhead of rectifying column into
Row level-one condenses, and the gas-phase product through level-one condensation carries out B-grade condensation, and the condensed liquid product of level-one is sent into level-one reflux
Tank, the gas-phase product discharge through B-grade condensation, liquid product after B-grade condensation are back to rectifying column again through two level return tank, and one
Product section in grade return tank is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product；Rectifying
The bottom of tower of tower is connected with reboiler.
Wherein, rectifying tower pressure on top surface is 3 ~ 4 kPa, and tower top temperature is 97 ~ 105 DEG C, 99 ~ 113 DEG C of column bottom temperature；Level-one
Condensing condition：Temperature control is 70 ~ 71 DEG C, gas phase fraction is 8%, B-grade condensation condition：Temperature control is 35 ~ 37 DEG C, and level-one is returned
The extraction and reflux ratio for flowing tank are 1：1.0.
Embodiment 6
A kind of process for purification of N-Methyl pyrrolidone product, includes the following steps：
It will need the N-Methyl pyrrolidone of purification（Raw material）Be sent into rectifying column and distill, the overhead of rectifying column into
Row level-one condenses, and the gas-phase product through level-one condensation carries out B-grade condensation, and the condensed liquid product of level-one is sent into level-one reflux
Tank, the gas-phase product discharge through B-grade condensation, liquid product after B-grade condensation are back to rectifying column again through two level return tank, and one
Product section in grade return tank is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product；Rectifying
The bottom of tower of tower is connected with reboiler.
Wherein, rectifying tower pressure on top surface is 9 ~ 10 kPa, and tower top temperature is 124 ~ 128 DEG C, 126 ~ 133 DEG C of column bottom temperature；
Level-one condensing condition：Temperature control is 120 ~ 123 DEG C, gas phase fraction is 30%, B-grade condensation condition：Temperature control is 40 ~ 42
DEG C, the extraction of level-one return tank and reflux ratio are 1：1.4.
Embodiment 7
A kind of process for purification of N-Methyl pyrrolidone product, includes the following steps：
It will need the N-Methyl pyrrolidone of purification（Raw material）Be sent into rectifying column and distill, the overhead of rectifying column into
Row level-one condenses, and the gas-phase product through level-one condensation carries out B-grade condensation, and the condensed liquid product of level-one is sent into level-one reflux
Tank, the gas-phase product discharge through B-grade condensation, liquid product after B-grade condensation are back to rectifying column again through two level return tank, and one
Product section in grade return tank is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product；Rectifying
The bottom of tower of tower is connected with reboiler.
Wherein, rectifying tower pressure on top surface is 6 ~ 7 kPa, and tower top temperature is 114 ~ 117 DEG C, 116 ~ 121 DEG C of column bottom temperature；One
Grade condensing condition：Temperature control is 110 ~ 112 DEG C, gas phase fraction is 40%, B-grade condensation condition：Temperature control is 45 ~ 47 DEG C,
The extraction of level-one return tank and reflux ratio are 1：1.4.
Embodiment 8
A kind of process for purification of N-Methyl pyrrolidone product, includes the following steps：
It will need the N-Methyl pyrrolidone of purification（Raw material）Be sent into rectifying column and distill, the overhead of rectifying column into
Row level-one condenses, and the gas-phase product through level-one condensation carries out B-grade condensation, and the condensed liquid product of level-one is sent into level-one reflux
Tank, the gas-phase product discharge through B-grade condensation, liquid product after B-grade condensation are back to rectifying column again through two level return tank, and one
Product section in grade return tank is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product；Rectifying
The bottom of tower of tower is connected with reboiler.
Wherein, rectifying tower pressure on top surface is 6 ~ 7 kPa, and tower top temperature is 114 ~ 117 DEG C, 116 ~ 121 DEG C of column bottom temperature；One
Grade condensing condition：Temperature control is 111 ~ 114 DEG C, gas phase fraction is 50%, B-grade condensation condition：Temperature control is 48 ~ 50 DEG C,
The extraction of level-one return tank and reflux ratio are 1：2.0.
Comparative example 1
In the technique of embodiment 1, the liquid phase part after B-grade condensation is produced, comparison product 1 is denoted as, specifically includes following step
Suddenly：
It will need the N-Methyl pyrrolidone of purification（Raw material）Be sent into rectifying column and distill, the overhead of rectifying column into
Row level-one condenses, and the gas-phase product through level-one condensation carries out B-grade condensation, and the condensed liquid product of level-one is sent into level-one reflux
Tank, the gas-phase product through B-grade condensation are discharged, and the liquid product after B-grade condensation is sent into two level return tank；In level-one return tank
Product section is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product, the production in two level return tank
Product are partly refluxed to rectifying column, while N-Methyl pyrrolidone product produces as a contrast for part；The bottom of tower of rectifying column is connected with
Reboiler.
Wherein, rectifying tower pressure on top surface is 4 ~ 5 kPa, and tower top temperature is 104 ~ 110 DEG C, 106 ~ 120 DEG C of column bottom temperature；One
Grade condensing condition：Temperature control is 95 ~ 100 DEG C, gas phase fraction is 10%, B-grade condensation condition：Temperature control be 30 ~ 32 DEG C, one
The extraction of grade return tank and reflux ratio are 1：0.8, the extraction of two level return tank and reflux ratio are 1：1.0, two level return tank
The sample of extraction is comparison product 1.
Comparative example 2
In the technique of embodiment 2, the liquid phase part after B-grade condensation is produced, comparison product 2 is denoted as, specifically includes following step
Suddenly：
It will need the N-Methyl pyrrolidone of purification（Raw material）Be sent into rectifying column and distill, the overhead of rectifying column into
Row level-one condenses, and the gas-phase product through level-one condensation carries out B-grade condensation, and the condensed liquid product of level-one is sent into level-one reflux
Tank, the gas-phase product through B-grade condensation are discharged, and the liquid product after B-grade condensation is sent into two level return tank；In level-one return tank
Product section is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product, the production in two level return tank
Product are partly refluxed to rectifying column, while N-Methyl pyrrolidone product produces as a contrast for part；The bottom of tower of rectifying column is connected with
Reboiler.
Wherein, rectifying tower pressure on top surface is 3 ~ 4 kPa, and tower top temperature is 97 ~ 105 DEG C, 101 ~ 115 DEG C of column bottom temperature；One
Grade condensing condition：Temperature control is 95 ~ 98 DEG C, gas phase fraction is 15%, B-grade condensation condition：Temperature control be 28 ~ 30 DEG C, one
The extraction of grade return tank and reflux ratio are 1：0.4, the extraction of two level return tank and reflux ratio are 1：2.0.
Comparative example 3
It will need the N-Methyl pyrrolidone of purification（Thick N-Methyl pyrrolidone is after de- amine and dehydration）Using common
Rectifying mode directly flows back and produces, condensation using conventional complete condenser or close to complete condenser state, in continuous feed and
Tower top pressure is 2 ~ 3 kPa（Absolute pressure）In the case of, cooling water is fully open, and tower top cooling temperature is 32 ~ 33 DEG C, is adopted from return tank
The ratio for going out and flowing back is 1：2, extraction product is denoted as comparison product 3.
It will need the N-Methyl pyrrolidone of purification（Raw material）, comparison product 1 ~ 3, embodiment 1 and embodiment 2 obtain
The product form of N-Methyl pyrrolidone product is detected, and the results are shown in Table 1.
1 each product form of table is analyzed
In table 1, the content of unhindered amina is with the content meter of methylamine, and light miscellaneous content is with the content meter of tetrahydrofuran, NMP（N- methyl
Pyrrolidones）In terms of wt%, impurity is in terms of ppm（Ppm is by weight）.By table 1 as it can be seen that being obtained using conventional rectification and purification method
To N-Methyl pyrrolidone in unhindered amina and light miscellaneous content it is higher, the N- methyl pyrroles produced after B-grade condensation of the present invention
Unhindered amina and light miscellaneous content are also higher in pyrrolidone, and the N-Methyl pyrrolidone obtained using the present invention is substantially better than comparison product
1 ~ 3, unhindered amina and light miscellaneous content are extremely low.
After testing, the N-Methyl pyrrolidone product quality indicator that embodiment 3 ~ 8 obtains is as follows：
Purity >=99.9%（wt%）, the ppm of unhindered amina≤5, light miscellaneous≤0.1 ppm.
Claims (8)
1. a kind of N-Methyl pyrrolidone process for purification, it is characterised in that：N-Methyl pyrrolidone product rectifier is arranged
One fractional condensaion system, the fractional condensaion system include two or more controllable temperatures heat exchanger and corresponding time
Flow tank.
2. N-Methyl pyrrolidone process for purification according to claim 1, it is characterised in that：The fractional condensaion system packet
First order heat exchanger and second level heat exchanger are included, first order heat exchanger is connected with level-one return tank；The rectifying column tower top distillates
Object is condensed by first order heat exchanger, and control outlet streams temperature is 50 ~ 120 DEG C, the condensed liquid phase production of first order heat exchanger
Object enters level-one return tank, is all produced as finished product, or part produces as finished product, is partly refluxed to rectifying column；The first order
The condensed gas-phase product of heat exchanger is condensed by second level heat exchanger, and control outlet streams temperature is room temperature ~ 50 DEG C, the second level
The condensed product infinite reflux of heat exchanger is to rectifying column；Wherein, the rectifying tower pressure on top surface control is 1 ~ 10kpa（Absolute pressure）,
The gas phase fraction of the first order heat exchanger is 0.50 ~ 0.02.
3. N-Methyl pyrrolidone process for purification according to claim 2, it is characterised in that：First order heat exchanger gas phase point
Rate is 0.40 ~ 0.05.
4. N-Methyl pyrrolidone process for purification according to claim 2, it is characterised in that：First order heat exchanger gas phase point
Rate is 0.30 ~ 0.08.
5. N-Methyl pyrrolidone process for purification according to claim 2, it is characterised in that：First order return tank produce and
Reflux ratio is 1:0~2.0.
6. N-Methyl pyrrolidone process for purification according to claim 2, it is characterised in that：First order return tank produce and
Reflux ratio is 1:0~1.0.
7. N-Methyl pyrrolidone process for purification according to claim 2, it is characterised in that：First order return tank produce and
Reflux ratio is 1:0~0.2.
8. N-Methyl pyrrolidone process for purification according to claim 1, it is characterised in that：N- methyl pyrrole in the finished product
Pyrrolidone has the characteristics that light miscellaneous and unhindered amina impurity is relatively low, and described is light miscellaneous less than 0.05wt%, and the unhindered amina total amount is low
In 5ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710287359.5A CN108794371B (en) | 2017-04-27 | 2017-04-27 | A kind of refining methd of N-Methyl pyrrolidone product |
Applications Claiming Priority (1)
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| CN112094217A (en) * | 2020-09-15 | 2020-12-18 | 安徽晟捷新能源科技有限公司 | Efficient and environment-friendly recovery device and method for N-methylpyrrolidone |
| CN113786639A (en) * | 2021-10-13 | 2021-12-14 | 中国天辰工程有限公司 | Quenching and dewatering process method for cyclohexanol dehydrogenation product |
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| CN111530472A (en) * | 2020-05-08 | 2020-08-14 | 迈奇化学股份有限公司 | Titanium-based heterogeneous amination composite catalyst and application thereof in production of N-methylpyrrolidone for liquid crystal panel |
| CN111530472B (en) * | 2020-05-08 | 2023-10-31 | 迈奇化学股份有限公司 | Titanium-based heterogeneous amination composite catalyst and application thereof in production of N-methylpyrrolidone for liquid crystal display panel |
| CN111423352A (en) * | 2020-05-19 | 2020-07-17 | 上海盛剑环境系统科技股份有限公司 | Recovery system and recovery method of N-methyl-2-pyrrolidone waste liquid |
| CN111423352B (en) * | 2020-05-19 | 2024-01-02 | 上海盛剑环境系统科技股份有限公司 | Recovery system and recovery method for N-methyl-2-pyrrolidone waste liquid |
| CN111777539A (en) * | 2020-07-17 | 2020-10-16 | 滨州裕能化工有限公司 | Multi-effect rectification system and method of N-methyl pyrrolidone |
| CN112094217A (en) * | 2020-09-15 | 2020-12-18 | 安徽晟捷新能源科技有限公司 | Efficient and environment-friendly recovery device and method for N-methylpyrrolidone |
| CN113786639A (en) * | 2021-10-13 | 2021-12-14 | 中国天辰工程有限公司 | Quenching and dewatering process method for cyclohexanol dehydrogenation product |
| CN117510390A (en) * | 2024-01-08 | 2024-02-06 | 江苏天鹏电源有限公司 | Method and system for removing free ammonia in NMP |
| CN117510390B (en) * | 2024-01-08 | 2024-03-29 | 江苏天鹏电源有限公司 | Method and system for removing free ammonia in NMP |
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Denomination of invention: A Refinement Method for N-Methylpyrrolidone Product Effective date of registration: 20230724 Granted publication date: 20190806 Pledgee: Bank of China Limited by Share Ltd. Puyang branch Pledgor: MYJ CHEMICAL CO.,LTD. Registration number: Y2023980049672 |