CN104072419B - The purification process of a kind of caprolactam and purification devices - Google Patents
The purification process of a kind of caprolactam and purification devices Download PDFInfo
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- CN104072419B CN104072419B CN201310516515.2A CN201310516515A CN104072419B CN 104072419 B CN104072419 B CN 104072419B CN 201310516515 A CN201310516515 A CN 201310516515A CN 104072419 B CN104072419 B CN 104072419B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
The purification process of a kind of caprolactam and purification devices.The method includes crystallization, water extraction, hydrogenation, dehydration by evaporation process, is not required to solid-liquid separation, can produce high-quality ε caprolactam product, is particularly suitable for the refined of the thick ε caprolactam that vapour phase rearrangement obtains.The caprolactam purification devices that the present invention provides, including the crystallizer being sequentially connected with, countercurrent washer, split-phase separator, hydrogenation reactor and distillation equipment；Simple in construction, can operate continuously, it is adaptable to the purge process of crude caprolactam.
Description
Technical field
The present invention relates to preparation method and the device of epsilon-caprolactams.More particularly, it relates to containing miscellaneous
The method of purification of the crude epsi-caprolactam of matter and purifying plant.
Background technology
Epsilon-caprolactams (hereinafter referred to as caprolactam) is the important monomer of synthetic fibers and synthetic resin,
Mainly for the manufacture of Fypro (nylon 6), resin and thin film etc..Known caprolactam production
Method includes using oleum as the cyclohexanone-oxime liquid phase Beckmann rearrangement method of catalyst, with solid
Zeolite is the methods such as cyclohexanone-oxime gas phase beckmann rearrangement method and the waste polymer depolymerization of catalyst.
Caprolactam prepared by these methods inevitably all contains the organic impurities of huge number, these
What impurity was serious have impact on the quality of caprolactam, therefore, must pass through purification process before application.
Known caprolactam purification include rectification, extract, adsorb, hydrogenate, aoxidize, the method such as crystallization.
Wherein crystallization process is effectively to remove one of most effectual way of multiclass impurity in caprolactam.
A kind of method disclosing refined caprolactam in US2813858, is to add in crude caprolactam
Enter a certain amount of water or the fusing point organic hydrocarbon solvent less than caprolactam, by be repeated several times crystallization, from
The process purifying caprolactam such as heart separation and washing.
US3966712 discloses the purification process of crude caprolactam prepared by a kind of vapour phase rearrangement method,
It is addition oxolane, isopropanol polar solvent in crude caprolactam, cooled crystallization, filter
Washing, adds alkali distillation and carrys out purifying caprolactam.
CN1332158A discloses the purification process of another kind of crude caprolactam, is by the fat of low temperature
Fat varsol is poured into container together with crude caprolactam, makes both mix and crystallizes, then dividing through solid-liquid
From process purifying crude caprolactams such as, crystal washings.
CN101070298A discloses the purification process of another kind of crude caprolactam, is by thick own interior
Amide crystallizes in ethereal solution, then through the process purifying crude caprolactam such as filtration washing, hydrogenation.
CN101070299A discloses the purification process of another kind of crude caprolactam, is by thick own interior
Amide crystallizes in halohydrocarbon solution, then through the process purifying crude caprolactam such as filtration washing, hydrogenation.
Although said method has good effect to purifying caprolactam, but true during practical application in industry
All suffer from crystal and the solid-liquid separation of mother solution and crystal washing and filtering problem.Existing solid-liquid is used to divide
From mode such as centrifugal filtration, filter pressing, vacuum filtration etc., not only process is loaded down with trivial details, investment is big, washing effect
Rate is low, and in operating, the caprolactam in mother solution is easy on filter plant wall separate out brilliant scar,
Cause operating difficulties.Particularly caprolactam, due to the characteristic that it is intrinsic, the crystal born is lamellar
Structure, intensity difference, broken, make solid-liquid separation and washing and filtering become more difficult, thus limit
The extensive application of crystallization process.
Summary of the invention
One of the technical problem to be solved in the present invention is to provide a kind of continuous print and is prone to the own of industrializing implementation
Lactams purification process.The method is not required to numerous and diverse solid-liquid separation system, it is easy to industrial implementation.
The two of the technical problem to be solved in the present invention are to provide a kind of simple in construction, and can operate continuously is thick
Caprolactam purification devices.
A kind of purification process of epsilon-caprolactams, including:
(1) in the presence of solvent orange 2 A, the crude epsi-caprolactam containing impurity is crystallized, obtain containing solvent
The magma of A；
(2) with solvent B, the magma obtained in step (1) is washed, obtain containing solvent B's
Wash rear magma and mother solution；
(3) the rear magma of washing obtained in step (2) is dissolved in water, split-phase obtain organic facies and ε-
Caprolactam water solution；
(4) in the presence of a hydrogenation catalyst, epsilon-caprolactam water solution is made to contact with hydrogen, distillation
Remove moisture content therein, obtain epsilon-caprolactams.
Preferably, the organic facies obtained in step (3) is preferably returned to step (2) and reuses；Step
Suddenly the moisture content reclaimed in (4) is preferably returned to step (3) and reuses.
Having the beneficial effect that of the caprolactam purification process that the present invention provides
The method that the present invention provides includes that the crystallization of crude caprolactam, countercurrent washing separate with solvent, can
Produce high-quality epsilon-caprolactams product.The essence of the crude epsi-caprolactam that applicable vapour phase rearrangement obtains
System.
A kind of caprolactam purification devices, including the crystallizer being sequentially connected with, countercurrent washer, split-phase
Separator, hydrogenation reactor and distillation equipment；Wherein, described crystallizer for stirring autoclave crystallizer,
Double-pipe chiller, draft tube baffle crystallizer or OSLO crystallizer；Described countercurrent washer be outer wall with
The countercurrent washer of tracing thermal-insulating；Described split-phase separator is layering tank or extraction tower；Described steaming
The equipment of evaporating is distillation column or flash tank.
Wherein, described crystallizer and countercurrent washer are independently arranged or integrally disposed.
Having the beneficial effect that of a kind of caprolactam purification devices that the present invention provides
A kind of caprolactam purification devices simple in construction that the present invention provides, easy to operate.Can be used for thick
The purification of caprolactam, obtains high-quality caprolactam product.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of a kind of embodiment of the inventive method.
In this embodiment, crystallization and countercurrent washing are independently arranged.
Fig. 2 is the schematic flow sheet of the another embodiment of the inventive method.
In this embodiment, crystallization and countercurrent washing are integrally disposed.
Fig. 3 is the principle schematic of a kind of countercurrent washer of the inventive method.
Fig. 4 is the structural representation that countercurrent washer is integrated with kettle type crystallization device.
Symbol description:
1--------crystallizer 7--------inner sleeve
2--------countercurrent washer 8--------agitator
3--------heater a--------magma entrance
4--------mother liquor tank b--------mother solution (the first liquid phase) exports
5--------circulating pump c---------cleaning solvent entrance
6--------cooler d---------washes the outlet of rear magma
Detailed description of the invention
The detailed description of the invention of the present invention described further below:
A kind of purification process of epsilon-caprolactams, including:
(1) in the presence of solvent orange 2 A, the crude epsi-caprolactam containing impurity is crystallized, obtain containing solvent
The magma of A；
(2) with solvent B, the magma obtained in step (1) is washed, obtain containing solvent B's
Wash rear magma and mother solution；
(3) the rear magma of washing obtained in step (2) is dissolved in water, split-phase obtain organic facies and ε-
Caprolactam water solution；
(4) in the presence of a hydrogenation catalyst, epsilon-caprolactam water solution is made to contact with hydrogen, distillation
Remove moisture content therein, obtain epsilon-caprolactams.
Preferably, the organic facies obtained in step (3) is preferably returned to step (2) and reuses；Step
Suddenly the moisture content reclaimed in (4) is preferably returned to step (3) and reuses.
In the method that the present invention provides, step (1) is by impure crude caprolactam and solvent orange 2 A
It is continuously introduced in crystallizer crystallization, obtains the caprolactam magma containing solvent orange 2 A.
The method that crystallization preferably employs recrystallization in organic solvent, is so more beneficial for the removal of impurity.
Crystallizer can be the most traditional stirring autoclave crystallizer, double-pipe chiller, draft tube baffle crystallizer and
OSLO crystallizer, pipettes for crystallization heat, and solvent well known to those skilled in the art can be used to steam
Send out and take heat, cooling takes heat and low-temperature material chilling takes the modes such as heat, and the present invention does not limits.
Described solvent orange 2 A is the recrystallisation solvent in step (1), selected to caprolactam solvability
Low organic solvent.This kind solvent include but not limited to aliphatic hydrocarbon, ethers, cycloalkane, aromatic hydrocarbon,
Halogenated hydrocarbons etc., consider from crystallization yield and solvent recovery angle, the preferred carbon number of solvent orange 2 A is 6-12
Aliphatic hydrocarbon, cycloalkane, aromatic hydrocarbon, organic ether and halogenated hydrocarbons in one or more.Above-mentioned solvent
Boiling point typically at 50 DEG C to 150 DEG C
The consumption of described solvent orange 2 A has influence on yield and the quality of caprolactam, with the weight of caprolactam
Gauge, generally 0.1 to 4 weight portions, preferably 0.3 to 3 weight portions, more preferably 0.5 to 2 weights
Amount part.
For traditional method for crystallising, due to needs solid-liquid separation, the crystal grain that consequently it is desirable to
Big and uniform, and for the present invention, due to the mode of washing that it is special, solid-liquid separation mistake can be avoided
Journey, does not therefore have strict requirements to grain size.The condition of crystallization becomes loose, and crystallization temperature can be
0 DEG C to 60 DEG C, temperature preferably is 10 DEG C to 58 DEG C, and stir speed (S.S.) also can be accelerated, in order to obtain
Purer caprolactam product.
In the method that the present invention provides, step (2) obtains with in solvent B washing step (1)
Magma, obtains washing rear magma and mother solution containing solvent B.The preferred countercurrent washing of described washing, refers to
Epsilon-caprolactams crystal from up to down, cleaning solvent bottom-up continuous flow upstream contact.
Described countercurrent washing is carried out in countercurrent washer.Accompanying drawing 3 is a kind of countercurrent washer
Structure principle chart, as shown in Figure 3, countercurrent washer includes charging aperture a, mother liquor outlet b, washing
Colvent inlet c exports d with washing rear magma.Magma from crystallizer sends into scrubber from charging aperture a,
Crystal the most from up to down moves, and forms crystal bed, for washing in scrubber
Solvent is continuously introduced into scrubber from c mouth, and some is bottom-up flows through crystal bed, by crystal gap
Between the mother solution continuous print carried secretly displace bed, the mother liquor outlet b from top flows out, remaining washing
Solvent is then discharged from bottom d mouth with the crystal after washing.
When application is amplified in industry, for preferably ensureing clean result, stirring can be installed in countercurrent washer
Device, magma feed distributor, cleaning solvent feed distributor, for crystal and the radial distribution of solvent.
It addition, for preventing cooling from causing wall to form brilliant scar, countercurrent washer outer wall needs tracing thermal-insulating,
Heat tracing form can be this specialty be familiar with heat tracing pipe or jacket hot tracing.
In the method that the present invention provides, in step (2), the solvent B of washing can be with step (1)
In recrystallisation solvent A identical, it is also possible to different, the described preferred carbon number of solvent B is 6-12
Aliphatic hydrocarbon, cycloalkane, aromatic hydrocarbon, organic ether and halogenated hydrocarbons in one or more.More preferably carbon
Atomic number is one or more in the aliphatic hydrocarbon of 7-9.The boiling point of above-mentioned solvent is at 50 DEG C to 150 DEG C.
Considering from reducing the solution loss of caprolactam crystal washing process, cleaning solvent B more preferably uses
The alkane that carbon number is 6-12 that dissolubility is low.
In step (2), if cleaning solvent B use the bigger cycloalkane of polarity, aromatic hydrocarbon,
Organic ether or halogenated hydrocarbons, be preferably used caprolactam and reach the saturated solution of dissolution equilibrium.According to use
Medium and the difference of wash temperature, the caprolactam content in cleaning solvent, in terms of weight of solvent, washs
Solvent contains the caprolactam of 0～0.8 weight portion, preferably 0～0.5 weight portion, more preferably 0～0.3 weight
Amount part.Preferably the temperature of cleaning solvent is-10 DEG C to 60 DEG C.
In step (2), the consumption of cleaning solvent B is made up of two parts, and one is upwards washing crystal
Part, two be with crystal discharge part.In the case of meeting clean result, wash in principle
The consumption of solvent is the lowest more good.For ensureing clean result, in terms of epsilon-caprolactams crystal weight, step
(2) in, the amount of solvent B is not less than 0.4 amount part, the more preferably amount of solvent B and is not less than 0.7 weight portion.
Wherein, the quantity of solvent for this part of washing crystal is typically not less than 0.1 weight portion, the lowest
In 0.2 weight portion.The quantity of solvent discharged with crystal depends on the magma concentration wanting extraction, with extraction
Crystal weight meter, preferably not less than 0.3 weight portion, more desirably not less than 0.5 weight portion.
On technological process arranges, countercurrent washer can be the most only with crystallizer
Erect and put, it is also possible to be the most integrally disposed.It is independently arranged and is applicable to and any type of knot
Brilliant device is combined, and integrally disposed being more suitable for is tied with kettle type crystallization device, draft tube baffle crystallizer and OSLO
The combination of brilliant device.Fig. 4 is the structural representation that countercurrent washer is integrated with kettle type crystallization device.With Fig. 4
Shown kettle type crystallization device and countercurrent washer integrally disposed as a example by, crystallization and countercurrent washing be describeds
Detailed process: after crude caprolactam and recrystallisation solvent are sufficiently mixed with circulating mother liquor, cooled device 6 is cold
But, forming the supersaturated solution of caprolactam, send in crystallizer 1 and crystallize, the crystal grown up is at weight
Power effect is lowered in countercurrent washer 2, from up to down moves, and bottom countercurrent washer, c mouth leads to
Entering cleaning solvent, a part of cleaning solvent is bottom-up flows through crystal bed, carries secretly by between crystal gap
Mother solution continuous print displace bed, mother liquor outlet b from crystallizer top flows out, remaining washing
Solvent is then discharged from bottom d mouth with the crystal after washing.The mother solution (the first liquid phase) flowed out from b mouth
Heater via 3 heating flows into mother liquor tank 4, and mother solution boosts through circulating pump 5, a part of as circulation mother
Liquid returns crystallizer, and remaining sends crystal system.
In the method that the present invention provides, step (3) is to be added by the rear magma of washing obtained in step (2)
Water dissolution, split-phase obtains organic facies and epsilon-caprolactam water solution.Add the amount of water, with caprolactam
Meter, preferably 0.1 to 2.5 weight portions, more preferably 0.1 to 0.4 weight portion.What split-phase obtained has
Machine can return solvent system mutually and recycle, it is preferable that described organic facies returns step (2)
Scrubber uses as cleaning solvent.
In the method that the present invention provides, step (4) is to be hydrogenated with by above-mentioned caprolactam water solution, distillation
Remove moisture content therein, obtain highly purified epsilon-caprolactams.
Described hydrogenation refers to contact with hydrogen in the presence of a hydrogenation catalyst, cannot will take off in crystallization process
The impurity removed is removed by hydrogenation.Suitable hydrogenation catalyst includes amorphous nickel catalyst, Raney
Raney nickel, it is loaded with the loaded catalyst of platinum or palladium.Suitable hydrogenation reactor form includes slurry
Bed reactor, fluidized-bed reactor, fixed bed reactors and magnetically stabilized bed reactor.Preferably,
The operating condition of hydrogenation is: reaction temperature is 65 DEG C-120 DEG C, and pressure is 0.5MPa-2.0MPa.
In the method that the present invention provides, after caprolactam water solution hydrogenation, also need to distill out water therein.
For avoid caprolactam because of the generation oligomer that is heated, during dehydration by evaporation, bottom temperature no more than
150 DEG C, consider from reducing energy consumption, it is preferred to use 2 to 4 distillation equipmenies, at different distillation pressure
Under, utilize the principle of multiple-effect evaporation first by aqueous solution concentration to about 90%, then it is (residual to carry out fine vacuum
Pressure about 1.3KPa) remove remaining moisture content.The water steamed is preferably returned to step (3) and reuses.
For crystalline mother solution, can process as follows: Distillation recovery solvent therein, and obtain
The caprolactam mother solution concentrated, the mother solution concentrated is crystallized by the method identical by the present invention, obtains
Solvent-laden magma, with solvent counter current washes, the magma after being washed, will wash rear magma and dissolve, return
Return step (1) and carry out recrystallization.
The method provided according to the present invention, described crystallization, countercurrent washing, dissolving and solvent distillation
Arbitrary process can be continuous print, it is also possible to be interval, it is preferred to use continuous operation.
The advantage of the preferred implementation of the purification process of a kind of caprolactam that the present invention provides is:
The method that the present invention provides includes crystallization, countercurrent washing and solvent evaporation, it is not necessary to solid-liquid separation.
Additionally crystallization condition is loose, and crystallization temperature can be at 0 DEG C to 60 DEG C, and in crystallizer, stir speed (S.S.) also can add
Hurry up, purification efficiency is high, can obtain purer epsilon-caprolactams product.It is particularly suitable for vapour phase rearrangement to obtain
Refining of the thick-epsilon-caprolactams arrived.
A kind of caprolactam purification devices, including the crystallizer being sequentially connected with, countercurrent washer, split-phase
Separator, hydrogenation reactor and distillation equipment；Wherein, described crystallizer for stirring autoclave crystallizer,
Double-pipe chiller, draft tube baffle crystallizer or OSLO crystallizer；Described countercurrent washer be outer wall with
The countercurrent washer of tracing thermal-insulating；Described split-phase separator is layering tank or extraction tower；Described steaming
The equipment of evaporating is distillation column or flash tank.
Wherein, described crystallizer is independently arranged with countercurrent washer or integrally disposed.
Preferably, agitator, magma feed distributor are set in described countercurrent washer and wash molten
Agent feed distributor.
The explanation present invention provides referring to the drawings caprolactam purification process and device, but the present invention
The most any way limited.
Fig. 1 is the schematic flow sheet of a kind of preferred implementation of the inventive method.As it is shown in figure 1,
Enter in crystallizer after mixing containing impurity crude caprolactam and solvent orange 2 A and crystallize, obtain containing solvent
The magma of A；Magma enters in scrubber and flows downward, and solvent B is entered countercurrent washer by bottom,
Flowing from bottom to top is washed with magma counter current contacting, obtains washing rear magma and crystalline mother solution containing solvent B,
Crystalline mother solution discharger.Add water to wash and rear magma dissolves caprolactam crystal, stratification,
Obtaining the aqueous solution of organic phase solvent B and caprolactam, separate organic facies and aqueous phase, isolated have
Machine returns mutually in countercurrent washer and reuses as cleaning solvent B；Isolated caprolactam is water-soluble
Liquid enters the impurity that in hydrogenation reactor, hydrogenation and removing wherein remains, the caprolactam water solution after hydrogenation
Carrying out therein moisture is distilled off, obtain caprolactam after purification, the water steamed is preferably returned to molten
Solve in hierarchical operations and reuse.In accompanying drawing 1, crystallizer and countercurrent washer are independently arranged.
Fig. 2 is the schematic flow sheet of the another kind of preferred implementation of the inventive method, and in accompanying drawing 1
Except for the difference that, crystallization and countercurrent washing are integrally disposed.
Further illustrate caprolactam purification process and effect that the present invention provides by the following examples.But
The present invention is not by its any restriction.
In embodiment, represent the % of amount, as being weight standard without special marking.
Following method of testing is used to evaluate the ε-own interior acyl of crystallization raw material and preparation in the examples below
Amine crystal and the quality of epsilon-caprolactams product:
(1) purity of epsilon-caprolactams
Use capillary column Innowax60m, gas chromatogram 7890GC, analyze epsilon-caprolactams purity and
Impurity content, chromatograph lowest detectable limit 1 μ g/g.
(2) the potassium permanganate absorption value (PM) of epsilon-caprolactams
The epsilon-caprolactams of 3.000 grams is poured in the color comparison tube of 100ml, add distilled water diluting to carving
Degree, shakes up, puts in the constant temperature water bath of 20.0 DEG C, and the concentration adding 1ml in color comparison tube is 0.01N
Potassium permanganate solution, shake up immediately, start stopwatch simultaneously, when the color of sample solution in color comparison tube
(3.000 grams of top grade pure Co (NO are taken with standard color solution3)2·6H2O and 12 milligrams of pure K of top grade2Cr2O7
Be dissolved in water, be diluted to 1 liter, shake up) color identical time stop stopwatch, write down consumed time (with
Second calculates), it is potassium permanganate absorption value.
(3) volatile base (V.B)
In alkaline medium, the alkaline low molecule impurity in sample is distilled, with the hydrochloric acid of known quantity
Solution absorbs, the hydrochloric acid standard solution of sodium hydroxide residual titration of excess.With every kilogram of sample acid consumption
Molal quantity is as the measured value of volatile base.Computing formula is as follows:
V.B(mmol/kg)=[(V0-V)×CNaOH/M]×1000
In formula: V0For the volume of the NaOH standard solution that blank assay consumes, unit is ml；
V is the volume of the NaOH standard solution that sample consumes, and unit is ml；
CNaOHFor the actual concentrations of NaOH standard solution, unit is mol/L；
M is sample quality, and unit is g.
(4) extinction value E(is at 290nm wavelength)
In 300ml conical flask, weigh the sample of 50 grams, add 50ml distilled water, shake up and make sample
Product are completely dissolved, and stand 10 minutes.Use spectrophotometer, under the wavelength of 290nm, detection
Concentration is that the sample of 50% is relative to the extinction value of distilled water.
Crude caprolactam in embodiment is to be obtained through distillation by vapour phase rearrangement product, has following group
Become:
Caprolactam: 99.60%, cyclohexanone-oxime: 33 μ g/g, N-methyl Tetrahydrobenzimidazderivative: 380 μ g/g,
Octahydro azophenlyene: 405 μ g/g.
Embodiment 1
Take 600 grams of crude caprolactams and 600 grams of diisopropyl ethers join the 2L glass with stirring and chuck
In still, it is passed through hot water heating in chuck to 70 degree, until caprolactam all dissolves, under agitation,
By the water temperature in regulation chuck, progressively it is cooled to 20 DEG C, obtains the magma of caprolactam.
Above-mentioned magma is proceeded to interior in the 20mm height 200mm column scrubber with chuck, connect from bottom
Continuous being passed through 1140 grams of (2 times of solvents) room temperature normal heptane and carry out countercurrent washing, mother solution is extracted out from top.
Magma concentration after washing is about 50%, and proceed to add water in 2L separatory funnel mix homogeneously, and room temperature is quiet
Put sedimentation, separate caprolactam water solution from bottom, proceed in 2L autoclave, add 5 grams of loads 2
The powdery hydrogenation catalyst (prepared by the method provided by patent 201010296075.0) of % palladium, heating
To 85 DEG C, it is subsequently passed hydrogen and boosts to 0.7MPa and carry out hydroprocessing 1.5 hours, be cooled to 60 DEG C
Left and right, is all pressed into material in intermittent column.Being decompressed to 1.3kPa dehydration by evaporation, tower reactor obtains
The caprolactam of purification 546 grams.The caprolactam taking a small amount of purification carries out chromatography, caprolactam
Purity is 99.997%, and wherein cyclohexanone-oxime, N-methyl Tetrahydrobenzimidazderivative, octahydro azophenlyene are not all examined
Go out.PM value 38000s, V.B value 0.20mmol/kg, E value 0.040.
Embodiment 2
150 grams of diisopropyl ethers and 450 grams of normal heptane are made into mixed solvent, take 200 grams of mixed solvents and add
In the 2L crystallization kettle with stirring and chuck, chuck is passed through hot water makes temperature in the kettle rise to 80 DEG C,
Take 400 grams of crude caprolactams and 400 grams of mixed solvent mix homogeneously at 40 DEG C, progressively drip under stirring
Enter crystallization kettle intercrystalline, obtain the magma of caprolactam.
Column scrubber chuck is passed through 40 DEG C of hot water, and above-mentioned magma is proceeded to column scrubber, and (1 times molten to take 380 grams
Agent) normal heptane and 11 grams of pure caprolactams, at 40 DEG C, it is made into saturated solution, bottom column scrubber
Being passed through continuously and carry out countercurrent washing, mother solution is extracted out from top.
The method identical by embodiment 1 carries out subsequent operation, obtains purifying caprolactam 383 grams, sampling
Analyzing composition, caprolactam purity is 99.995%, wherein cyclohexanone-oxime, N-methyl tetrahydro benzo miaow
Azoles, octahydro azophenlyene all do not detect.PM value 35000s, V.B value 0.30mmol/kg, E value 0.040.
Claims (16)
1. the purification process of an epsilon-caprolactams, it is characterised in that including:
(1) in the presence of solvent orange 2 A, the crude epsi-caprolactam containing impurity is crystallized, obtain containing solvent
The magma of A；
(2) with solvent B, the magma obtained in step (1) is washed, obtain containing solvent B's
Wash rear magma and mother solution；
(3) the rear magma of washing obtained in step (2) is dissolved in water, split-phase obtain organic facies and ε-
Caprolactam water solution；
(4) in the presence of a hydrogenation catalyst, epsilon-caprolactam water solution is made to contact with hydrogen, distillation
Reclaim moisture content therein, obtain epsilon-caprolactams；
Described solvent orange 2 A be carbon number be the aliphatic hydrocarbon of 6-12, cycloalkane, aromatic hydrocarbon, halogenated hydrocarbons
With one or more in organic ether；Described solvent B be carbon number be the aliphatic hydrocarbon of 6-12, ring
One or more in alkane, aromatic hydrocarbon, halogenated hydrocarbons and organic ether.
Method the most according to claim 1, it is characterised in that in terms of the weight of caprolactam, described
The consumption of solvent orange 2 A be 0.1 to 4 weight portions.
Method the most according to claim 2, it is characterised in that in terms of the weight of caprolactam, described
The consumption of solvent orange 2 A be 0.3 to 3 weight portions.
Method the most according to claim 3, it is characterised in that in terms of the weight of caprolactam, described
The consumption of solvent orange 2 A be 0.5 to 2 weight portions.
Method the most according to claim 1, it is characterised in that in step (1), crystallization temperature is 0 DEG C
To 60 DEG C.
Method the most according to claim 1, it is characterised in that described in step (2), washing is for inverse
Stream washing, refer to epsilon-caprolactams crystal from up to down, the bottom-up continuous flow upstream of cleaning solvent connects
Touch.
Method the most according to claim 1, it is characterised in that described solvent B is carbon number
For one or more in the aliphatic hydrocarbon of 7-9.
Method the most according to claim 1, it is characterised in that in terms of epsilon-caprolactams crystal weight,
In step (2), the amount of solvent B is not less than 0.4 weight portion.
Method the most according to claim 8, it is characterised in that in terms of epsilon-caprolactams crystal weight,
In step (2), the amount of solvent B is not less than 0.7 weight portion.
Method the most according to claim 1, it is characterised in that the operation temperature of washing in step (2)
Degree is for-10 DEG C to 60 DEG C.
11. methods according to claim 1, it is characterised in that in terms of caprolactam weight, step
(3) amount adding water in is 0.1 to 2.5 weight portions.
12. methods according to claim 11, it is characterised in that in terms of caprolactam weight, step
(3) amount adding water in is 0.1 to 0.4 weight portion.
13. methods according to claim 1, it is characterised in that the organic facies obtained in step (3)
Return in step (2) and use as solvent.
14. 1 kinds of caprolactam purification devices, it is characterised in that the crystallizer that includes being sequentially connected with,
Countercurrent washer, split-phase separator, hydrogenation reactor and distillation equipment；Wherein, described crystallizer
For stirring autoclave crystallizer, double-pipe chiller, draft tube baffle crystallizer or OSLO crystallizer；Described is inverse
Stream scrubber is the outer wall countercurrent washer with tracing thermal-insulating；Described split-phase separator is layering tank
Or extraction tower；Described distillation equipment is distillation column or flash tank.
15. devices according to claim 14, it is characterised in that described crystallizer and countercurrent washing
Device is independently arranged or integrally disposed.
16. devices according to claim 14, it is characterised in that arrange in described countercurrent washer
Agitator, magma feed distributor and cleaning solvent feed distributor.
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| CN105622510A (en) * | 2014-11-04 | 2016-06-01 | 中国石油化工股份有限公司 | Refining method of caprolactam |
| CN106250694B (en) * | 2016-08-01 | 2019-01-29 | 浙江中控软件技术有限公司 | A kind of the quality index flexible measurement method and device of caprolactam product |
| CN109665997B (en) * | 2017-10-17 | 2021-01-08 | 中国石油化工股份有限公司 | Preparation method of caprolactam |
| CN109665980B (en) * | 2017-10-17 | 2021-01-08 | 中国石油化工股份有限公司 | Refining method of caprolactam |
| CN109665995B (en) * | 2017-10-17 | 2023-01-13 | 中国石油化工股份有限公司 | Refining method of caprolactam crude product and preparation method of caprolactam |
| CN109721537B (en) * | 2017-10-30 | 2021-01-08 | 中国石油化工股份有限公司 | Refining method of caprolactam |
| CN109721520B (en) * | 2017-10-30 | 2021-01-08 | 中国石油化工股份有限公司 | Refining method of caprolactam |
| CZ308473B6 (en) * | 2018-11-27 | 2020-09-09 | Vysoká škola chemicko-technologická v Praze | Method for isolation of ɛ-caprolactam from the upper lactam phase |
| CN111686477B (en) * | 2020-06-30 | 2022-07-29 | 聊城鲁西聚酰胺新材料科技有限公司 | Caprolactam extraction liquid washing tower, system and process |
| CN116023316A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Process for producing high purity epsilon-caprolactam |
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