CN108794371B - A kind of refining methd of N-Methyl pyrrolidone product - Google Patents
A kind of refining methd of N-Methyl pyrrolidone product Download PDFInfo
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- CN108794371B CN108794371B CN201710287359.5A CN201710287359A CN108794371B CN 108794371 B CN108794371 B CN 108794371B CN 201710287359 A CN201710287359 A CN 201710287359A CN 108794371 B CN108794371 B CN 108794371B
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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 refining methds 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 and corresponding return tank of two or more controllable temperatures, it is distilled specifically includes the following steps: the N-Methyl pyrrolidone for needing purification is sent into rectifying column, the overhead of rectifying column carries out level-one condensation, secondary heat exchanger condensation is sent into 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, product section in level-one return tank is back to rectifying column, part is produced as N-Methyl pyrrolidone purified product simultaneously.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 refining methd of N-Methyl pyrrolidone product.
Background technique
Pyrrolidones is a kind of product category for being widely used in the industries such as solvent, chemical industry, medicine, includes N- methyl pyrrole
Pyrrolidone (NMP), N- ethyl pyrrolidone (NEP) etc., wherein NMP and NEP is that the polarity that selectivity is strong, stability is good is molten
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, the solvent of many engineering plastics (polyvinylidene fluoride etc.), the electrode of lithium ion battery are auxiliary
Material is helped, photoresist removes liquid, the production of LCD liquid crystal material, 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 is the preparation method comprises the following steps: using gamma-butyrolacton and methylamine (40%)
Thermal condensation reaction is carried out with the molar ratio of 1:1.10 ~ 1.20, then concentrated and vacuum distillation can obtain the finished product of purity > 99%.
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 require methylamine content≤5ppm, moisture in product to contain
≤ 0.02%, pH is measured between 7-9, coloration≤10.Gamma-butyrolacton is used in existing production technology and monomethylamine aqueous solution is original
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 cause in electronics, medicine in downstream application simultaneously
There is potential deviation.Therefore the method for purification for developing new N-Methyl pyrrolidone product, the N- methylpyrrole after purifying it
The requirement that alkanone purity and its impurity content (such as methylamine content) can satisfy 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 with ion-exchange as Chinese patent application CN102001986A and CN102190611A are disclosed
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 method for this two patent application publications uses
It is more, complicated for operation, and treatment effeciency is lower, or needs to increase organic alcohols, causes to N-Methyl pyrrolidone product
Secondary pollution.Patent CN201310019294.8 discloses the method that de- unhindered amina is adsorbed using ion-exchange fibre, exists fine
It is lower 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.
In order to optimize technique working condition, production cost is reduced to greatest extent, realizes mentioning for N-Methyl pyrrolidone product
Sublimate produces high-quality N-Methyl pyrrolidone product, how to select specific process flow and equipment very crucial.
Summary of the invention
The purpose of the present invention is to provide a kind of refining methds 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 are as follows:
A kind of N-Methyl pyrrolidone refining methd, it is cold that a classification is arranged in N-Methyl pyrrolidone product rectifier
Solidifying system, the fractional condensaion system includes the heat exchanger and corresponding return tank of two or more controllable temperatures.
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 top of the distillation column 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
Producing mouthful stream temperature is room temperature ~ 50 DEG C, the condensed product infinite reflux of second level heat exchanger to rectifying column；Wherein, the essence
Evaporating the control of column overhead pressure is 1 ~ 10kpa(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 lower in the finished product, described
Light miscellaneous lower than 0.05wt%, the unhindered amina total amount is lower 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 is distilled the following steps are included: the N-Methyl pyrrolidone for needing purification is sent into rectifying column, 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
Product whole extraction in return tank or the product section in level-one return tank are back to rectifying column, while part is used as N- first
The extraction of base pyrrolidones purified product.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 be 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 test and theoretical examination discovery, unhindered amina such as monomethyl amine, formamide, dimethylamine etc. are 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 DEG C) and can be destroyed, so that the free amine content in NMP product 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 dissolution, the unhindered amina total amount in NMP product and phase fraction of working off one's feeling vent one's spleen have it is inevitable contact,
And by test with caution, opereating specification of the present invention is obtained.
Wherein, gas phase fraction (Vapor Fraction) 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.The pressure and tower top of NMP product tower/kettle temperature degree condition be it is well known in the art, such as it is white
Heptan is pungent to write<1,4-butanediol, tetrahydrofuran and its derivative>, and the second section of chapter 4 describes in detail in Chemical Industry Press.
For the present invention, preferred rectifying tower pressure on top surface (absolute pressure) is 1 ~ 10 kPa, and tower top temperature is 95 ~ 128 DEG C, tower bottom temperature
97 ~ 160 DEG C of degree.
The present invention is excessively high for unhindered amina impurity content in prior art N-Methyl pyrrolidone, is not able to satisfy SEMI C12
Requirement and granular ion exchange resin and ion-exchange fibre low efficiency, 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, can simply and efficiently be gone
It except unhindered amina in N-Methyl pyrrolidone, and can further remove in N-Methyl pyrrolidone light miscellaneous, invest that 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 DEG C) 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
The requirement of amine, volatile components and moisture technical indicator considerably beyond electronics (SEMI C12) and 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 from the regulation in 0.1 ~ 5ppm, while further decreasing the light miscellaneous content of finished product, to improve product purity.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Specific embodiment
In order to keep technical purpose of the invention, technical scheme and beneficial effects clearer, combined with specific embodiments below
Technical solution of the present invention is further illustrated, but the embodiment is intended to explain the present invention, and should not be understood as pair
Limitation of the 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 refining methd of N-Methyl pyrrolidone product, comprising the following steps:
It is distilled as shown in Figure 1, the N-Methyl pyrrolidone (raw material) for needing purification is sent into rectifying column 1, rectifying
The overhead of tower 1 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 carry out B-grade condensation, and the condensed liquid product of level-one is sent into level-one return tank 4, the gas-phase product discharge through B-grade condensation, and two
The condensed liquid product of grade is back to rectifying column 1 through second level return tank 5 again, and the product section in level-one return tank 4 is back to
Rectifying column 1, while part is as N-Methyl pyrrolidone purified product extraction (entering finished pot 6)；The tower bottom of rectifying column 1 is connected with
Reboiler 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 refining methd of N-Methyl pyrrolidone product, comprising the following steps:
The N-Methyl pyrrolidone (raw material) for needing purification is sent into rectifying column and is distilled, the tower top of rectifying column distillates
Object carries out level-one condensation, 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
Return tank, the gas-phase product through B-grade condensation are discharged, and the liquid product after B-grade condensation is back to rectifying through second level return tank again
Tower, the product section in level-one return tank is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product；
The tower bottom 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 be 95 ~ 98 DEG C, gas phase fraction be 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 refining methd of N-Methyl pyrrolidone product, comprising the following steps:
The N-Methyl pyrrolidone (raw material) for needing purification is sent into rectifying column and is distilled, the tower top of rectifying column distillates
Object carries out level-one condensation, 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
Return tank, the gas-phase product through B-grade condensation are discharged, and the liquid product after B-grade condensation is back to rectifying through second level return tank again
Tower, the product section in level-one return tank is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product；
The tower bottom of rectifying column 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 refining methd of N-Methyl pyrrolidone product, comprising the following steps:
The N-Methyl pyrrolidone (raw material) for needing purification is sent into rectifying column and is distilled, the tower top of rectifying column distillates
Object carries out level-one condensation, 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
Return tank, the gas-phase product through B-grade condensation are discharged, and the liquid product after B-grade condensation is back to rectifying through second level return tank again
Tower, the product section in level-one return tank is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product；
The tower bottom of rectifying column 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 refining methd of N-Methyl pyrrolidone product, comprising the following steps:
The N-Methyl pyrrolidone (raw material) for needing purification is sent into rectifying column and is distilled, the tower top of rectifying column distillates
Object carries out level-one condensation, 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
Return tank, the gas-phase product through B-grade condensation are discharged, and the liquid product after B-grade condensation is back to rectifying through second level return tank again
Tower, the product section in level-one return tank is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product；
The tower bottom 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, 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 refining methd of N-Methyl pyrrolidone product, comprising the following steps:
The N-Methyl pyrrolidone (raw material) for needing purification is sent into rectifying column and is distilled, the tower top of rectifying column distillates
Object carries out level-one condensation, 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
Return tank, the gas-phase product through B-grade condensation are discharged, and the liquid product after B-grade condensation is back to rectifying through second level return tank again
Tower, the product section in level-one return tank is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product；
The tower bottom of rectifying column 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 refining methd of N-Methyl pyrrolidone product, comprising the following steps:
The N-Methyl pyrrolidone (raw material) for needing purification is sent into rectifying column and is distilled, the tower top of rectifying column distillates
Object carries out level-one condensation, 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
Return tank, the gas-phase product through B-grade condensation are discharged, and the liquid product after B-grade condensation is back to rectifying through second level return tank again
Tower, the product section in level-one return tank is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product；
The tower bottom of rectifying column 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 refining methd of N-Methyl pyrrolidone product, comprising the following steps:
The N-Methyl pyrrolidone (raw material) for needing purification is sent into rectifying column and is distilled, the tower top of rectifying column distillates
Object carries out level-one condensation, 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
Return tank, the gas-phase product through B-grade condensation are discharged, and the liquid product after B-grade condensation is back to rectifying through second level return tank again
Tower, the product section in level-one return tank is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product；
The tower bottom of rectifying column 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:
The N-Methyl pyrrolidone (raw material) for needing purification is sent into rectifying column and is distilled, the tower top of rectifying column distillates
Object carries out level-one condensation, 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
Return tank, the gas-phase product through B-grade condensation are discharged, and the liquid product after B-grade condensation is sent into second level return tank；Level-one return tank
Interior product section is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product, in second level return tank
Product section be back to rectifying column, while part is as control N-Methyl pyrrolidone product extraction；The tower bottom of rectifying column connects
It is connected to 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 be 95 ~ 100 DEG C, gas phase fraction be 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, and the extraction of second level return tank and reflux ratio are 1:1.0, second 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:
The N-Methyl pyrrolidone (raw material) for needing purification is sent into rectifying column and is distilled, the tower top of rectifying column distillates
Object carries out level-one condensation, 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
Return tank, the gas-phase product through B-grade condensation are discharged, and the liquid product after B-grade condensation is sent into second level return tank；Level-one return tank
Interior product section is back to rectifying column, while part is produced as N-Methyl pyrrolidone purified product, in second level return tank
Product section be back to rectifying column, while part is as control N-Methyl pyrrolidone product extraction；The tower bottom of rectifying column connects
It is connected to 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 be 95 ~ 98 DEG C, gas phase fraction be 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, and the extraction of second level return tank and reflux ratio are 1:2.0.
Comparative example 3
The N-Methyl pyrrolidone (thick N-Methyl pyrrolidone is after de- amine and dehydration) of purification will be needed using general
Logical rectifying mode directly flows back and produces, condensation using conventional complete condenser or close to complete condenser state, continuously into
Material and tower top pressure are 2 ~ 3 kPa(absolute pressures) in the case of, cooling water is fully open, and tower top cooling temperature is 32 ~ 33 DEG C, from reflux
The ratio of tank extraction and reflux is 1:2, and extraction product is denoted as comparison product 3.
The N-Methyl pyrrolidone (raw material) for needing purification, comparison product 1 ~ 3, embodiment 1 and embodiment 2 are obtained
The product form of N-Methyl pyrrolidone product is detected, and the results are shown in Table 1.
The analysis of each product form of table 1
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 pyrrolidone) in terms of wt%, impurity (ppm is by weight) in terms of ppm.Seen from table 1, using conventional rectification and purification side
Unhindered amina and light miscellaneous content are higher in the N-Methyl pyrrolidone that method obtains, the N- first produced after B-grade condensation of the present invention
Unhindered amina and light miscellaneous content are also higher in base pyrrolidones, are substantially better than pair using the N-Methyl pyrrolidone that the present invention obtains
Than product 1 ~ 3, unhindered amina and light miscellaneous content are extremely low.
Through detecting, the N-Methyl pyrrolidone product quality indicator that embodiment 3 ~ 8 obtains is as follows:
Purity >=99.9%(wt%), unhindered amina≤5 ppm, light miscellaneous≤0.1 ppm.
Claims (7)
1. a kind of N-Methyl pyrrolidone refining methd, it is characterised in that: the setting of N-Methyl pyrrolidone product rectifier
One fractional condensaion system, the fractional condensaion system include two or more controllable temperatures heat exchanger and corresponding time
Flow tank；
The fractional condensaion system includes first order heat exchanger and second level heat exchanger, and first order heat exchanger is connected with level-one reflux
Tank；The top of the distillation column distillate is condensed by first order heat exchanger, and control outlet streams temperature is 50 ~ 120 DEG C, the first order
The condensed liquid product of heat exchanger enters level-one return tank, all produces as finished product, or part is as finished product extraction, part
It is back to rectifying column；The condensed gas-phase product of first order heat exchanger is condensed by second level heat exchanger, controls outlet streams temperature
Degree is room temperature ~ 50 DEG C, the condensed product infinite reflux of second level heat exchanger to rectifying column；Wherein, the rectifying tower pressure on top surface
Control is 1 ~ 10kPa, and the gas phase fraction of the first order heat exchanger is 0.02 ~ 0.50.
2. N-Methyl pyrrolidone refining methd according to claim 1, it is characterised in that: first order heat exchanger gas phase point
Rate is 0.05 ~ 0.40.
3. N-Methyl pyrrolidone refining methd according to claim 1, it is characterised in that: first order heat exchanger gas phase point
Rate is 0.08 ~ 0.30.
4. N-Methyl pyrrolidone refining methd according to claim 1, it is characterised in that: the first order return tank extraction and
Reflux ratio is 1:0 ~ 2.0.
5. N-Methyl pyrrolidone refining methd according to claim 1, it is characterised in that: the first order return tank extraction and
Reflux ratio is 1:0 ~ 1.0.
6. N-Methyl pyrrolidone refining methd according to claim 1, it is characterised in that: the first order return tank extraction and
Reflux ratio is 1:0 ~ 0.2.
7. N-Methyl pyrrolidone refining methd according to claim 1, it is characterised in that: N-Methyl pyrrolidone has
The light miscellaneous and lower feature of unhindered amina impurity, described is light miscellaneous lower than 0.05wt%, and the unhindered amina total amount is lower than 5ppm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710287359.5A CN108794371B (en) | 2017-04-27 | 2017-04-27 | A kind of refining methd of N-Methyl pyrrolidone product |
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| CN201710287359.5A CN108794371B (en) | 2017-04-27 | 2017-04-27 | A kind of refining methd of N-Methyl pyrrolidone product |
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| KR102474740B1 (en) * | 2018-12-18 | 2022-12-05 | 주식회사 엘지화학 | Process for recovering amide compounds |
| CN110922347B (en) * | 2019-12-02 | 2022-12-06 | 山东京博聚芳新材料股份有限公司 | Method for separating N-methyl pyrrolidone from large-amount chloroform system |
| CN111138336A (en) * | 2019-12-31 | 2020-05-12 | 江苏中德电子材料科技有限公司 | Efficient, energy-saving and environment-friendly continuous production process of ultra-clean high-purity N-methyl pyrrolidone |
| CN111974411A (en) * | 2020-05-08 | 2020-11-24 | 迈奇化学股份有限公司 | Titanium-based heterogeneous amination composite catalyst and preparation method and application thereof |
| 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 |
| CN111777539B (en) * | 2020-07-17 | 2022-02-11 | 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 |
| 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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