CN104072419A - Purification method and purification device of caprolactam - Google Patents
Purification method and purification device of caprolactam Download PDFInfo
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- CN104072419A CN104072419A CN201310516515.2A CN201310516515A CN104072419A CN 104072419 A CN104072419 A CN 104072419A CN 201310516515 A CN201310516515 A CN 201310516515A CN 104072419 A CN104072419 A CN 104072419A
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- C07—ORGANIC CHEMISTRY
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- 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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Abstract
The invention discloses a purification method and a purification device of caprolactam. The method comprises process of crystallization, extraction in water, hydrogenation and evaporation dehydration, no solid-separation is needed, a high-quality epsilon-caprolactam product can be produced, and thus the method is particularly applicable to refining of crude epsilon-caprolactam obtained through gas phase rearrangement. The caprolactam purification device disclosed by the invention comprises a crystallizer, a countercurrent washer, a phase separator, a hydrogenation reactor and distillation equipment which are connected in sequence. The device is simple in structure, capable of continuous operation and applicable to a purification process of crude caprolactam.
Description
Technical field
The present invention relates to preparation method and the device of ε-caprolactam.More particularly, relate to method of purification and the purifying plant of the crude epsi-caprolactam that contains impurity.
Background technology
ε-caprolactam (hereinafter to be referred as hexanolactam) is the important monomer of synthon and synthetic resins, mainly for the manufacture of tynex (nylon 6), resin and film etc.Known caprolactam production method comprises that employing oleum is as the cyclohexanone-oxime liquid phase Beckmann rearrangement method of catalyzer, the method such as cyclohexanone-oxime gas phase beckmann rearrangement method and waste polymer depolymerization taking solid zeolite as catalyzer.In hexanolactam prepared by these methods, inevitably all contain the numerous organic impurity of kind, the impact that these impurity are serious the quality of hexanolactam, therefore, essential through purification process before application.Known hexanolactam purifying comprises the methods such as rectifying, extraction, absorption, hydrogenation, oxidation, crystallization.Wherein crystallization process is one of most effectual way of multiclass impurity in effective elimination hexanolactam.
In US2813858, disclosing a kind of method of refined caprolactam, is in crude caprolactam, to add a certain amount of water or the fusing point organic hydrocarbon solvent lower than hexanolactam, by repeatedly repeating the process purifying hexanolactams such as crystallization, centrifugation and washing.
In US3966712, disclosing the purification process of the standby crude caprolactam of a kind of vapor phase rearrangement legal system, is in crude caprolactam, to add tetrahydrofuran (THF), Virahol isopolarity solvent, and through crystallisation by cooling, filtration washing, adds alkali and distill purifying hexanolactam.
In CN1332158A, disclosing the purification process of another kind of crude caprolactam, is by the fat hydrocarbon solvent of low temperature impouring container together with crude caprolactam, both is mixed and crystallization, then through process purifying crude caprolactams such as solid-liquid separation, crystal washings.
In CN101070298A, disclosing the purification process of another kind of crude caprolactam, is by crude caprolactam crystallization in ethereal solution, then the process purifying crude caprolactam such as washing, hydrogenation after filtration.
In CN101070299A, disclosing the purification process of another kind of crude caprolactam, is by crude caprolactam crystallization in halohydrocarbon solution, then the process purifying crude caprolactam such as washing, hydrogenation after filtration.
Although aforesaid method has good effect to purifying hexanolactam, when practical application in industry, really all face solid-liquid separation and the crystal washing and filtering problem of crystal and mother liquor.Adopt existing solid-liquid separation method as centrifuging, press filtration, vacuum filtration etc., not only process is loaded down with trivial details, investment is large, detersive efficiency is low, and in operation, the hexanolactam in mother liquor is easy to separate out brilliant scar on filter plant wall, causes operational difficulty.Particularly hexanolactam, due to its intrinsic characteristic, the crystal of bearing is sheet structure, intensity difference is easily broken, makes solid-liquid separation and washing and filtering become more difficult, has limited thus the widespread use 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 hexanolactam purification process that is easy to industrializing implementation.The method does not need numerous and diverse solid-liquid separation system, is easy to industrial implementation.
Two of the technical problem to be solved in the present invention is to provide a kind of simple in structure, crude caprolactam purification devices that can operate continuously.
A purification process for ε-caprolactam, comprising:
(1) under solvent orange 2 A exists by the crude epsi-caprolactam crystallization that contains impurity, obtain the magma containing solvent orange 2 A;
(2) with solvent B, the magma obtaining in step (1) is washed, obtain washing rear magma and mother liquor containing solvent B;
(3) the rear magma of washing obtaining in step (2) is dissolved in water, phase-splitting obtains organic phase and epsilon-caprolactam water solution;
(4) under hydrogenation catalyst exists, epsilon-caprolactam water solution is contacted with hydrogen, distillation removes moisture content wherein, obtains ε-caprolactam.
Preferably, the organic phase obtaining in step (3) is preferably returned to step (2) and is reused; The moisture content reclaiming in step (4) preferably returns to step (3) and reuses.
The beneficial effect of hexanolactam purification process provided by the invention is:
Method provided by the invention comprises crystallization, countercurrent washing and the separated from solvent of crude caprolactam, can produce high-quality ε-caprolactam product.Refining of the crude epsi-caprolactam that applicable vapor phase rearrangement obtains.
A kind of hexanolactam purification devices, comprises the crystallizer, countercurrent washer, point phase separator, hydrogenator and the distillation plant that connect successively; Wherein, described crystallizer is for stirring autoclave crystallizer, double-pipe crystallizer, draft tube baffle crystallizer or OSLO crystallizer; Described countercurrent washer is the countercurrent washer of outer wall with tracing thermal-insulating; A described point phase separator is layering tank or extraction tower; Described distillation plant is distillation tower or flash tank.
Wherein, described crystallizer and countercurrent washer independently arrange or integrated setting.
The beneficial effect of a kind of hexanolactam purification devices provided by the invention is:
A kind of hexanolactam purification devices provided by the invention is simple in structure, easy to operate.Can be used for the purifying of crude caprolactam, obtain high-quality caprolactam product.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of a kind of embodiment of the inventive method.
In this embodiment, crystallization and countercurrent washing independently arrange.
Fig. 2 is the schematic flow sheet of the another kind of embodiment of the inventive method.
The integrated setting of crystallization and countercurrent washing in this embodiment.
Fig. 3 is the principle schematic of a kind of countercurrent washer of the inventive method.
Fig. 4 is the integrated structural representation of countercurrent washer and kettle type crystallization device.
Nomenclature:
1--------crystallizer 7--------inner sleeve
2--------countercurrent washer 8--------agitator
3--------well heater a--------magma entrance
4--------mother liquor tank b--------mother liquor (the first liquid phase) outlet
5--------recycle pump c---------cleaning solvent entrance
6--------water cooler d---------washes rear magma outlet
Embodiment
Below describe the specific embodiment of the present invention in detail:
A purification process for ε-caprolactam, comprising:
(1) under solvent orange 2 A exists by the crude epsi-caprolactam crystallization that contains impurity, obtain the magma containing solvent orange 2 A;
(2) with solvent B, the magma obtaining in step (1) is washed, obtain washing rear magma and mother liquor containing solvent B;
(3) the rear magma of washing obtaining in step (2) is dissolved in water, phase-splitting obtains organic phase and epsilon-caprolactam water solution;
(4) under hydrogenation catalyst exists, epsilon-caprolactam water solution is contacted with hydrogen, distillation removes moisture content wherein, obtains ε-caprolactam.
Preferably, the organic phase obtaining in step (3) is preferably returned to step (2) and is reused; The moisture content reclaiming in step (4) preferably returns to step (3) and reuses.
In method provided by the invention, step (1) is that impure crude caprolactam and solvent orange 2 A are sent into crystallization in crystallizer continuously, obtains the hexanolactam magma containing solvent orange 2 A.
Crystallization preferably adopts the method for recrystallization in organic solvent, is so more conducive to the removal of impurity.Crystallizer can be optionally traditional stirring autoclave crystallizer, double-pipe crystallizer, draft tube baffle crystallizer and OSLO crystallizer, for pipetting of heat of crystallization, can adopt the modes such as solvent evaporation heat-obtaining, cooling heat-obtaining and low-temperature material chilling heat-obtaining well known to those skilled in the art, the present invention does not limit.
Described solvent orange 2 A is the recrystallisation solvent in step (1), is selected from the organic solvent low to hexanolactam dissolving power.This kind solvent includes but not limited to aliphatic hydrocarbon, ethers, naphthenic hydrocarbon, aromatic hydrocarbon, halohydrocarbon etc., consider one or more in aliphatic hydrocarbon, naphthenic hydrocarbon, aromatic hydrocarbon, organic ether and halohydrocarbon that the preferred carbonatoms of solvent orange 2 A is 6-12 from crystallization yield and solvent recuperation angle.The boiling point of above-mentioned solvent is generally at 50 DEG C to 150 DEG C
The consumption of described solvent orange 2 A has influence on yield and the quality of hexanolactam, with the weighing scale of hexanolactam, is generally 0.1 to 4 weight part, preferably 0.3 to 3 weight part, more preferably 0.5 to 2 weight part.
For traditional crystallization method, due to needs solid-liquid separation, therefore wish that the crystal grain obtaining is large and even, and for the present invention, due to its special mode of washing, can avoid solid-liquid separation process therefore grain size is not had to strict requirement.The condition of crystallization becomes loose, and Tc can be 0 DEG C to 60 DEG C, and temperature preferably is 10 DEG C to 58 DEG C, and stir speed (S.S.) also can be accelerated, to obtain purer caprolactam product.
In method provided by the invention, step (2) is the magma obtaining with in solvent B washing step (1), obtains washing rear magma and mother liquor containing solvent B.The preferred countercurrent washing of described washing, refer to ε-caprolactam crystal from up to down, the contact of the bottom-up continuous countercurrent of cleaning solvent.
Described countercurrent washing is carried out in countercurrent washer.Accompanying drawing 3 is structure principle charts of a kind of countercurrent washer, and as shown in Figure 3, countercurrent washer comprises opening for feed a, mother liquor outlet b, cleaning solvent entrance c and wash rear magma outlet d.Magma from crystallizer is sent into washer from opening for feed a, crystal from up to down moves under action of gravity, in washer, form crystal bed, send into continuously washer for the solvent washing from c mouth, the a part of bottom-up crystal bed that flows through, by the bed that the displaces continuous mother liquor of carrying secretly between crystal gap, flow out from the mother liquor outlet b on top, remaining cleaning solvent is discharged from bottom d mouth with the crystal after washing.
When application is amplified in industry, for better ensureing washing effect, agitator, magma feed distributor, cleaning solvent feed distributor can be installed, for the radial distribution of crystal and solvent in countercurrent washer.In addition, for preventing that cooling from causing wall to form brilliant scar, countercurrent washer outer wall needs tracing thermal-insulating, and accompanying hot form can be the familiar trace pipe of this specialty or jacket hot tracing.
In method provided by the invention, in step (2), the solvent B of washing use can be identical with the recrystallisation solvent A in step (1), also can be different, one or more in aliphatic hydrocarbon, naphthenic hydrocarbon, aromatic hydrocarbon, organic ether and halohydrocarbon that the described preferred carbonatoms of solvent B is 6-12.More preferably one or more in the aliphatic hydrocarbon that carbonatoms is 7-9.The boiling point of above-mentioned solvent is at 50 DEG C to 150 DEG C.Consider from the solution loss that reduces hexanolactam crystal washing process, cleaning solvent B more preferably uses the alkane that carbonatoms that solubleness is low is 6-12.
In step (2), if cleaning solvent B uses larger naphthenic hydrocarbon, aromatic hydrocarbon, organic ether or the halohydrocarbon of polarity, preferably use hexanolactam to reach the saturated solution of dissolution equilibrium.According to the difference of working medium and wash temperature, the caprolactam content in cleaning solvent, in weight of solvent, contains the hexanolactam of 0～0.8 weight part in cleaning solvent, preferably 0～0.5 weight part, more preferably 0～0.3 weight part.The temperature of preferred cleaning solvent is-10 DEG C to 60 DEG C.
In step (2), the consumption of cleaning solvent B is made up of two portions, and the one, the upwards part of washing crystal, the 2nd, the part of discharging with crystal.In the situation that meeting washing effect, the consumption of cleaning solvent is more low better in principle.For ensureing washing effect, in ε-caprolactam crystal weight, in step (2), the amount of solvent B is not less than 0.4 amount part, more preferably the amount of solvent B is not less than 0.7 weight part.Wherein, for washing crystal this part quantity of solvent be generally not less than 0.1 weight part, be preferably not less than 0.2 weight part.The quantity of solvent of discharging with crystal depends on the magma concentration of wanting extraction, in the crystal weight of extraction, is preferably not less than 0.3 weight part, is more preferably not less than 0.5 weight part.
On technical process arranges, countercurrent washer and crystallizer can independently arrange as shown in Figure 3, also integrated setting as shown in Figure 4.Independent setting is applicable to any type of crystallizer combinedly, and integrated setting is more suitable for and the combination of kettle type crystallization device, draft tube baffle crystallizer and OSLO crystallizer.Fig. 4 is the integrated structural representation of countercurrent washer and kettle type crystallization device.With the integrated example that is set to of the kettle type crystallization device shown in Fig. 4 and countercurrent washer, the detailed process of crystallization and countercurrent washing is described: after crude caprolactam and recrystallisation solvent fully mix with circulating mother liquor, cooling through water cooler 6, form the supersaturated solution of hexanolactam, send into crystallization in crystallizer 1, the crystal of growing up is lowered in countercurrent washer 2 in action of gravity, from up to down move, pass into cleaning solvent from countercurrent washer bottom c mouth, the bottom-up crystal bed that flows through of a part of cleaning solvent, by the bed that the displaces continuous mother liquor of carrying secretly between crystal gap, flow out from the mother liquor outlet b on crystallizer top, remaining cleaning solvent is discharged from bottom d mouth with the crystal after washing.Mother liquor (the first liquid phase) heater via 3 heating of flowing out from b mouth flow into mother liquor tank 4, and mother liquor boosts through recycle pump 5, and some is returned to crystallizer as circulating mother liquor, and all the other send crystal system.
In method provided by the invention, step (3) is that the rear magma of washing obtaining in step (2) is dissolved in water, and phase-splitting obtains organic phase and epsilon-caprolactam water solution.Add the amount of water, in hexanolactam, be preferably 0.1 to 2.5 weight part, more preferably 0.1 to 0.4 weight part.The organic phase that phase-splitting obtains can be returned to solvent systems and recycle, and preferably, the washer that described organic phase is returned to step (2) uses as cleaning solvent.
In method provided by the invention, step (4) is by above-mentioned caprolactam water solution hydrogenation, and distillation removes moisture content wherein, obtains highly purified ε-caprolactam.
Described hydrogenation refers under hydrogenation catalyst exists and contacts with hydrogen, the impurity that cannot remove in crystallisation process is removed by hydrogenation.Suitable hydrogenation catalyst comprises amorphous nickel catalyzer, Raney nickel catalyzator, is loaded with the loaded catalyst of platinum or palladium.Suitable hydrogenator form comprises paste state bed reactor, fluidized-bed reactor, fixed-bed reactor and magnetically stabilized bed reactor.Preferably, the operational condition of hydrogenation is: temperature of reaction is 65 DEG C-120 DEG C, and pressure is 0.5MPa-2.0MPa.
In method provided by the invention, after caprolactam water solution hydrogenation, also need to distill out water wherein.For avoiding hexanolactam because being subject to thermogenesis oligopolymer, in dehydration by evaporation process, tower reactor temperature should not exceed 150 DEG C, consider from reducing energy consumption, preferably adopt 2 to 4 distillation plants, under different distillation pressure, the principle of utilizing multiple-effect evaporation first by aqueous solution concentrate to 90% left and right, then carry out high vacuum (residual voltage 1.3KPa left and right) and remove remaining moisture content.The water steaming preferably returns to step (3) and reuses.
For crystalline mother solution, can process as follows: Distillation recovery solvent wherein, and obtain concentrated hexanolactam mother liquor, by the method that the present invention is identical, concentrated mother liquor is carried out to crystallization, obtain solvent-laden magma, use solvent countercurrent washing, obtain the magma after washing, to wash rear magma and dissolve, and return to step (1) and carry out recrystallization.
According to method provided by the invention, arbitrary process of described crystallization, countercurrent washing, dissolving and solvent distillation can be continuous, can be also intermittently, preferably adopts operate continuously.
The advantage of the preferred implementation of the purification process of a kind of hexanolactam provided by the invention is:
Method provided by the invention comprises crystallization, countercurrent washing and solvent evaporation, does not need solid-liquid separation.Crystallization condition is loose in addition, and Tc can be at 0 DEG C to 60 DEG C, and in crystallizer, stir speed (S.S.) also can be accelerated, and purification efficiency is high, can obtain purer ε-caprolactam product.Be particularly suitable for that vapor phase rearrangement obtains thick-ε-caprolactam refining.
A kind of hexanolactam purification devices, comprises the crystallizer, countercurrent washer, point phase separator, hydrogenator and the distillation plant that connect successively; Wherein, described crystallizer is for stirring autoclave crystallizer, double-pipe crystallizer, draft tube baffle crystallizer or OSLO crystallizer; Described countercurrent washer is the countercurrent washer of outer wall with tracing thermal-insulating; A described point phase separator is layering tank or extraction tower; Described distillation plant is distillation tower or flash tank.
Wherein, described crystallizer and countercurrent washer independently arrange or integrated setting.
Preferably, agitator, magma feed distributor and cleaning solvent feed distributor are set in described countercurrent washer.
Referring to brief description of the drawings hexanolactam purification process provided by the invention and device, but therefore the present invention is not subject to any restriction.
Fig. 1 is the schematic flow sheet of a kind of preferred implementation of the inventive method.As shown in Figure 1, contain after impurity crude hexanolactam and solvent orange 2 A mix and enter in crystallizer and carry out crystallization, obtain the magma containing solvent orange 2 A; Magma enters in washer and flows downward, and solvent B enters countercurrent washer by bottom, flows and magma counter current contact washing from bottom to top, obtains washing rear magma and crystalline mother solution, crystalline mother solution discharger containing solvent B.Water is added to wash in rear magma and dissolve hexanolactam crystal, stratification, obtains the aqueous solution of organic phase solvent B and hexanolactam, separates organic phase and water, and isolated organic phase is returned in countercurrent washer and reused as cleaning solvent B; Isolated caprolactam water solution enters wherein residual impurity of hydrogenation and removing in hydrogenator, caprolactam water solution after hydrogenation distills the moisture of removing wherein, obtain the hexanolactam after purifying, the water steaming preferably returns to dissolve in hierarchical operations and reuses.In accompanying drawing 1, crystallizer and countercurrent washer independently arrange.
Fig. 2 is the schematic flow sheet of the another kind of preferred implementation of the inventive method, from different in accompanying drawing 1, and the integrated setting of crystallization and countercurrent washing.
Further illustrate by the following examples hexanolactam purification process provided by the invention and effect.But the present invention is not subject to its any restriction.
In embodiment, represent the % of amount, as being weight standard without special marking.
In following examples, evaluate the quality of ε-caprolactam crystal and the ε-caprolactam product of crystallization raw material and preparation by following testing method:
(1) purity of ε-caprolactam
Use capillary column Innowax60m, gas-chromatography 7890GC, purity and the foreign matter content of analysis ε-caprolactam, chromatogram lowest detectable limit 1 μ g/g.
(2) the potassium permanganate absorption value (PM) of ε-caprolactam
The ε-caprolactam of 3.000 grams is poured in the colorimetric cylinder of 100ml, adding distil water is diluted to scale, shake up, put into the constant temperature water bath of 20.0 DEG C, the potassium permanganate solution that is 0.01N to the concentration that adds 1ml in colorimetric cylinder, shake up immediately, start stopwatch simultaneously, when color and the standard color solution of sample solution in colorimetric cylinder (are got 3.000 grams of pure Co (NO of top grade
3)
26H
2o and 12 milligrams of pure K of top grade
2cr
2o
7water-soluble, be diluted to 1 liter, shake up) color stop stopwatch when identical, write down the consumed time (to calculate second), be potassium permanganate absorption value.
(3) volatile alkali (V.B)
In alkaline medium, low the alkalescence in sample molecular impurity is distilled, with the hydrochloric acid soln absorption of known quantity, excessive hydrochloric acid standard solution of sodium hydroxide residual titration.Measured value using the mole number of every kilogram of sample acid consumption as volatile alkali.Calculation formula is as follows:
V.B（mmol/kg）=[(V
0-V)×C
NaOH/M]×1000
In formula: V
0for the volume of NaOH standardized solution that blank test consumes, unit is ml;
V is the volume of the NaOH standardized solution of sample consumption, and unit is ml;
C
naOHfor the accurate concentration of NaOH standardized solution, unit is mol/L;
M is sample quality, and unit is g.
(4) extinction value E(is at 290nm wavelength)
In 300ml Erlenmeyer flask, take the sample of 50 grams, add 50ml distilled water, shake up sample is dissolved completely, leave standstill 10 minutes.Adopt spectrophotometer, under the wavelength of 290nm, the sample that detectable level is 50% is with respect to the extinction value of distilled water.
Crude caprolactam in embodiment is to be obtained through distillation by vapor phase rearrangement reaction product, has following composition:
Hexanolactam: 99.60%, cyclohexanone-oxime: 33 μ g/g, N-methyl Tetrahydrobenzimidazderivative: 380 μ g/g, octahydro azophenlyene: 405 μ g/g.
Embodiment 1
Get 600 grams of crude caprolactams and 600 grams of isopropyl ethers join with stir and the 2L glass kettle of chuck in, in chuck, pass into hot water heating to 70 degree, until hexanolactam all dissolves, under agitation, by regulating the water temperature in chuck, be progressively cooled to 20 DEG C, obtain the magma of hexanolactam.
Above-mentioned magma is proceeded to and interiorly, in the washing column with chuck, passes into continuously 1140 grams of (2 times of solvents) normal temperature normal heptanes carry out countercurrent washing from bottom through the high 200mm of 20mm, and mother liquor is extracted out from top.
Magma concentration after washing is about 50%, proceed in 2L separating funnel and add water and mix, normal temperature standing sedimentation, separate caprolactam water solution from bottom, proceed in 2L autoclave, the powdery hydrogenation catalyst (the method preparation providing by patent 201010296075.0) of 5 grams of load 2% palladiums is provided, be heated to 85 DEG C, pass into subsequently hydrogen and boost to 0.7MPa and carry out hydroprocessing 1.5 hours, be cooled to 60 DEG C of left and right, material is all pressed in intermittent column.Be decompressed to 1.3kPa dehydration by evaporation, tower reactor obtains 546 grams of the hexanolactams of purifying.The hexanolactam of purifying of taking a morsel carries out stratographic analysis, and hexanolactam purity is 99.997%, and wherein cyclohexanone-oxime, N-methyl Tetrahydrobenzimidazderivative, octahydro azophenlyene all do not detect.PM value 38000s, V.B value 0.20mmol/kg, E value 0.040.
Embodiment 2
150 grams of isopropyl ethers and 450 grams of normal heptanes are made into mixed solvent, getting 200 grams of mixed solvents joins in the crystallization kettle of 2L with stirring and chuck, chuck passes into hot water makes temperature in the kettle rise to 80 DEG C, get 400 grams of crude caprolactams and 400 grams of mixed solvents mix at 40 DEG C, under stirring, progressively splash into crystallization kettle intercrystalline, obtain the magma of hexanolactam.
Washing column chuck passes into 40 DEG C of hot water, and above-mentioned magma is proceeded to washing column, gets 380 grams of (1 times of solvent) normal heptanes and 11 grams of pure hexanolactams, at 40 DEG C, is made into saturated solution, passes into continuously and carries out countercurrent washing from washing column bottom, and mother liquor is extracted out from top.
Carry out subsequent operations by the method that embodiment 1 is identical, obtain 383 grams of purifying hexanolactams, sampling analysis composition, hexanolactam purity is 99.995%, wherein cyclohexanone-oxime, N-methyl Tetrahydrobenzimidazderivative, octahydro azophenlyene all do not detect.PM value 35000s, V.B value 0.30mmol/kg, E value 0.040.
Claims (18)
1. a purification process for ε-caprolactam, is characterized in that, comprising:
(1) under solvent orange 2 A exists by the crude epsi-caprolactam crystallization that contains impurity, obtain the magma containing solvent orange 2 A;
(2) with solvent B, the magma obtaining in step (1) is washed, obtain washing rear magma and mother liquor containing solvent B;
(3) the rear magma of washing obtaining in step (2) is dissolved in water, phase-splitting obtains organic phase and epsilon-caprolactam water solution;
(4) under hydrogenation catalyst exists, epsilon-caprolactam water solution is contacted with hydrogen, Distillation recovery moisture content wherein, obtains ε-caprolactam.
2. according to the method for claim 1, it is characterized in that, described solvent orange 2 A is that carbonatoms is one or more in aliphatic hydrocarbon, naphthenic hydrocarbon, aromatic hydrocarbon, halohydrocarbon and the organic ether of 6-12.
3. according to the method for claim 2, it is characterized in that, with the weighing scale of hexanolactam, the consumption of described solvent orange 2 A is 0.1 to 4 weight part.
4. according to the method for claim 3, it is characterized in that, with the weighing scale of hexanolactam, the consumption of described solvent orange 2 A is 0.3 to 3 weight part.
5. according to the method for claim 4, it is characterized in that, with the weighing scale of hexanolactam, the consumption of described solvent orange 2 A is 0.5 to 2 weight part.
6. according to the method for claim 1, it is characterized in that, in step (1), Tc is 0 DEG C to 60 DEG C.
7. according to the method for claim 1, it is characterized in that, washing described in step (2) is for countercurrent washing, refer to ε-caprolactam crystal from up to down, the bottom-up continuous countercurrent contact of cleaning solvent.
8. according to the method for claim 1, it is characterized in that, described solvent B is that carbonatoms is one or more in aliphatic hydrocarbon, naphthenic hydrocarbon, aromatic hydrocarbon, halohydrocarbon and the organic ether of 6-12.
9. method according to Claim 8, is characterized in that, described solvent B is that carbonatoms is one or more in the aliphatic hydrocarbon of 7-9.
10. according to the method for claim 1, it is characterized in that, in ε-caprolactam crystal weight, in step (2), the amount of solvent B is not less than 0.4 amount part.
11. according to the method for claim 10, it is characterized in that, in ε-caprolactam crystal weight, in step (2), the amount of solvent B is not less than 0.7 weight part.
12. according to the method for claim 1, it is characterized in that, in step (2), the service temperature of washing is-10 DEG C to 60 DEG C.
13. according to the method for claim 1, it is characterized in that, with hexanolactam weighing scale, the amount that adds water in step (3) is 0.1 to 2.5 weight part.
14. according to the method for claim 13, it is characterized in that, with hexanolactam weighing scale, the amount that adds water in step (3) is 0.1 to 0.4 weight part.
15. according to the method for claim 1, it is characterized in that, the organic phase obtaining in step (3) is returned in step (2) and used as solvent.
16. 1 kinds of hexanolactam purification devices, is characterized in that, comprise the crystallizer, countercurrent washer, point phase separator, hydrogenator and the distillation plant that connect successively; Wherein, described crystallizer is for stirring autoclave crystallizer, double-pipe crystallizer, draft tube baffle crystallizer or OSLO crystallizer; Described countercurrent washer is the countercurrent washer of outer wall with tracing thermal-insulating; Described phase-splitting knockout tower is layering tank or extraction tower; Described distillation plant is distillation tower or flash tank.
17. according to the device of claim 16, it is characterized in that, described crystallizer and countercurrent washer independently arrange or integrated setting.
18. according to the device of claim 16, it is characterized in that, agitator, magma feed distributor and cleaning solvent feed distributor are set in described countercurrent washer.
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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 |
| CN106250694A (en) * | 2016-08-01 | 2016-12-21 | 浙江中控软件技术有限公司 | The quality index flexible measurement method of a kind of caprolactam product and device |
| CN109665997A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | A kind of preparation method of caprolactam |
| CN109665980A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | A kind of refining methd of caprolactam |
| CN109665995A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | The refining methd of caprolactam crude product and the preparation method of caprolactam |
| CN109721520A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of refining methd of caprolactam |
| CN109721537A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of refining methd 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 |
| CN111686477A (en) * | 2020-06-30 | 2020-09-22 | 聊城鲁西聚酰胺新材料科技有限公司 | Caprolactam extraction liquid washing tower, system and process |
| WO2023072199A1 (en) * | 2021-10-27 | 2023-05-04 | 中国石油化工股份有限公司 | METHOD FOR PRODUCING HIGH-PURITY ε-CAPROLACTAM |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN106250694A (en) * | 2016-08-01 | 2016-12-21 | 浙江中控软件技术有限公司 | The quality index flexible measurement method of a kind of caprolactam product and device |
| 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 |
| CN109665997A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | A kind of preparation method of caprolactam |
| CN109665980A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | A kind of refining methd of caprolactam |
| CN109665995A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | The refining methd of caprolactam crude product and the preparation method of caprolactam |
| CN109721520A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of refining methd of caprolactam |
| CN109721537A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of refining methd 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 |
| 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 |
| CN111686477A (en) * | 2020-06-30 | 2020-09-22 | 聊城鲁西聚酰胺新材料科技有限公司 | Caprolactam extraction liquid washing tower, system and process |
| 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 |
| WO2023072199A1 (en) * | 2021-10-27 | 2023-05-04 | 中国石油化工股份有限公司 | METHOD FOR PRODUCING HIGH-PURITY ε-CAPROLACTAM |
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