CN109574928A - A method of purification cyclohexanone oxime vapour phase rearrangement product - Google Patents
A method of purification cyclohexanone oxime vapour phase rearrangement product Download PDFInfo
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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 present invention provides a kind of method for refining cyclohexanone oxime vapour phase rearrangement product, which is characterized in that cyclohexanone oxime vapour phase rearrangement product to be refined is dissolved in recrystallisation solvent, through crystallization, separation of solid and liquid after, obtains crude caprolactam；Crude caprolactam obtains refined caprolactam through desolventizing, distillation；The recrystallisation solvent includes main solvent and cosolvent；The main solvent is at least one of ether, hydro carbons, halogenated hydrocarbons；The cosolvent is alcohol.The method of the present invention is especially suitable for rearrangement reaction liquid desolventizing, dehydration, de- light impurity, without the de- cyclohexanone oxime vapour phase rearrangement product handled again.The method of above-mentioned purification cyclohexanone oxime vapour phase rearrangement product, process flow is simple, and product yield is high, and residuum is few, environmental-friendly.
Description
Technical field
The present invention relates to field of fine chemical, more particularly to a kind of method for refining cyclohexanone oxime vapour phase rearrangement product.
Background technique
Industrially manufacture caprolactam is so that cyclohexanone oxime is carried out liquid phase Beckman weight under oleum catalytic condition
Row reacts and generates caprolactam.Newer technique is cyclohexanone oxime under the catalysis of solid acid catalyst at present, gas phase into
Row Beckmann rearrangement generates caprolactam.Vapour phase rearrangement product contains caprolactam, water and various impurity, most process dehydration,
De- light, Tuo Chonghou, obtains the caprolactam of primary purification.It is taken off in weight in the third step of fractionation, tower bottoms is referred to as cyclohexanone
Oxime vapour phase rearrangement product fractionation weight raffinate, wherein being higher than the impurity of caprolactam containing caprolactam and boiling point, caprolactam exists
Content about 70~85% in weight raffinate, needs to recycle, to improve rearrangement process total recovery.
For example, the Chinese patent literature of Publication No. CN103420913A discloses a kind of crystal refining side of caprolactam
Method, by the solution of the crude product containing epsilon-caprolactams and the step of crystal seed contact treatment, described contact treatment is containing ε-acyl in oneself
It is carried out in the Metastable zone of the solution of amine crude product, described crystal seed is the caprolactam particle of 2~80 mesh.Publication No.
101070299 Chinese patent literature discloses a kind of separating-purifying refining methd of epsilon-caprolactams, specifically discloses and passes through
The step of further being refined under hydrogenation catalyst again after halogenated hydrocarbons purification.
The Chinese patent literature of Publication No. 101429148 discloses a kind of production method of epsilon-caprolactams, this method
The following steps are included: (1), in the presence of rearrangement reaction catalyst, cyclohexanone oxime alcoholic solution carries out gas phase Beckman in nitrogen atmosphere
Rearrangement reaction obtains the alcoholic solution containing crude epsi-caprolactam；(2) alcoholic solution containing crude epsi-caprolactam is distilled, is recycled
Alcohol is recycled, while obtaining the epsilon-caprolactams tower reactor mixture containing water, light impurity component, heavy seeds component；(3) will
(2) epsilon-caprolactams tower reactor mixture carries out distillation dehydration, obtains component containing light impurity, the mixing of the tower reactor of heavy seeds component
Object；(4) it carries out the tower reactor mixture that (3) obtain that light component is distilled off, it is molten that tower reactor obtains the epsilon-caprolactams containing heavy constituent
Liquid；(5) the epsilon-caprolactams solution containing heavy constituent that (4) obtain is distilled, heavy seeds component stays in tower reactor, periodically outer
Row obtains the epsilon-caprolactams of 99.2% or more purity by tower top；(6) ε-for 99.2% or more the purity for obtaining (5) oneself
Lactams is mixed with ethereal solution or halohydrocarbon solution, is recrystallized, and centrifuge separation obtains crystal epsilon-caprolactams；(7) will
(6) the crystal epsilon-caprolactams obtained carry out solvent washing, separation, obtain 99.99% or more crystal epsilon-caprolactams；(8)
Hydrogenation step: in the presence of a hydrogenation catalyst, the crystal epsilon-caprolactams and/or its aqueous solution for obtaining (7) are contacted with hydrogen
Reaction, the epsilon-caprolactams of the high-purity recycled.
At present in vapour phase rearrangement product purification method, related technique all includes vapour phase rearrangement product " de- weight " this step
Suddenly；It not only needs to expend a large amount of steam in distillation process, but also in the heavy raffinate that weight-removing column tower reactor generates, at least contains
70% or more caprolactam.In order to improve the total recovery of vapour phase rearrangement technique, then this part of caprolactam must be recycled, in
It is to need additional recyclable device and energy consumption；Also, the caprolactam of recycling, the country that can not reach caprolactam product are excellent
Grade product index.
Summary of the invention
To solve the shortcomings of the prior art, the present invention provides a kind of sides for refining cyclohexanone oxime vapour phase rearrangement product
Method, it is intended to simplify treatment process, improve the purity and yield of the caprolactam being refining to obtain.
A method of purification cyclohexanone oxime vapour phase rearrangement product, comprising the following steps:
By cyclohexanone oxime vapour phase rearrangement product to be refined, (to refined caprolactam crude product, the present invention is also referred to as reset
Product) it is dissolved in recrystallisation solvent, through crystallization, separation of solid and liquid after, obtain crude caprolactam (caprolactam of preliminary purification)；Slightly
Caprolactam obtains refined caprolactam through desolventizing, distillation；
The recrystallisation solvent includes main solvent and cosolvent；The main solvent be ether, hydro carbons, in halogenated hydrocarbons at least
It is a kind of；
The cosolvent is alcohol.
Through research, the inventor has found that by the main solvent and cosolvent coordinated as recrystallisation solvent, it can
The purity and yield for facilitating the caprolactam that promotion is refining to obtain help to simplify production technology, reduce production cost.
The method of the present invention can be applied to existing through de- weight treated rearrangement product；It can also be applied to after existing de- weight
Bottom product in recycle caprolactam；Especially suitable for without the de- rearrangement product handled again.
Preferably, the cyclohexanone oxime vapour phase rearrangement product is obtained by following steps:
Cyclohexanone oxime is passed through into gas phase beckmann rearrangement, obtains rearrangement reaction liquid；And
By the rearrangement reaction liquid desolventizing, dehydration, de- light impurity, the cyclohexanone oxime vapour phase rearrangement product is obtained.
The prior art multipair vapour phase rearrangement product greatly carries out desolventizing, dehydration, dehydrogenation and de- handles again.It is de- to handle again, be
In order to further enhance treated caprolactam purity, crystallization difficulty is further decreased.It is handled again however, take off, it can not
It avoids increasing processing cost, and it is not high to refine yield.In order to overcome the technical deficiency, the present inventor attempts to save to take off and walk again
Suddenly, but due to dealing with objects complicated component, technological development early stage, there are the purity of caprolactam and undesirable etc. difficulties of yield
Topic.To overcome the problem, the present inventor has found that in recrystallisation solvent, a certain proportion of cosolvent of compatibility can by numerous studies
Reach under the premise of saving de- weight step, high-purity that still can be unexpected, the purpose of the refined caprolactam of high-recovery.
After the present invention carries out desolventizing, dehydration, de- light impurity to rearrangement product, it is directly entered solvent crystallization unit, is removed
Weight-removing column, has saved investment and operating cost, and original process heavy raffinates to be treated is not present in technique of the invention.
In the present invention, existing method is can be used in cyclohexanone oxime vapour phase rearrangement method, to the reaction solution of rearrangement carry out desolventizing,
Dehydration, dehydrogenation and etc. existing conventional method can also be used.
Preferably, the boiling range of the main solvent is lower than 270 DEG C.The boiling range of main solvent of the present invention is no more than
The boiling point of caprolactam.
Further preferably, the solvent is propyl ether, butyl ether, Di Iso Propyl Ether, butyl ether, C6~C12Direct-connected alkane
Hydrocarbon, C6~C12Branched paraffin, C6~C12Cycloalkane, C6~C12Straight chain halogenated alkane, C6~C12Branch halogenated alkane
Or C6~C12Halogenated cycloalkane and its mixture.
Further preferably, the boiling range of the main solvent is 68~142 DEG C.Main solvent and cosolvent under the boiling range
Synergy is more preferable.
Still more preferably, at least one of Di Iso Propyl Ether, hexamethylene, n-hexane, chlorocyclohexane.
In the solvent that can be used, appropriate alcohols can be added to increase impurities exhibit.
Preferably, the boiling range of the cosolvent is lower than 100 DEG C.
Further preferably, the boiling range of the cosolvent is 40~80 DEG C.
Still more preferably, the cosolvent is methanol and/or ethyl alcohol.Using the solvent, effect is more excellent, for example,
Product purity is further promoted.
Preferably, cosolvent is the 0.1%~15% of main solvent weight percent.Studies have shown that in the knot of the content
Under brilliant solvent, the purity is high of product, and the ideal yield coefficient of product；Yield can be reduced to a certain degree higher than 15%.
Further preferably, cosolvent is the 0.5%~8% of the weight percent of main solvent.
Still more preferably, cosolvent is the 3%~6% of the weight percent of main solvent.Under the preferred ratio, produce
The purity and yield of object are further promoted, studies have shown that the purity for the caprolactam being refining to obtain can be higher than 99.99%.
Preferably, the mass ratio of the cyclohexanone oxime vapour phase rearrangement product and recrystallisation solvent is 4: 1~1: 3.Cooperation institute
The recrystallisation solvent stated to the greatest extent can may be used preferably under the range under the premise of caprolactam product for obtaining meeting national standard
The raising vapour phase rearrangement process overall yields of energy.Greater than the upper limit, the problems such as crystal quality is reduced with magma difficulty of transportation can be generated；It is small
In lower limit value, yield is reduced, crystallization process since it is desired that lower final temperature and cause energy consumption to increase.
Further preferably, the mass ratio of the cyclohexanone oxime vapour phase rearrangement product and recrystallisation solvent is 1~1.5: 1.Cooperation
The recrystallisation solvent, then control under the preferred scope, the purity of product reaches top grade level comprehensively, and yield further mentions
It rises.
By the control of the proportion recrystallisation solvent and solvent usage, preferred crystallization temperature is 15~60 DEG C.Cooperation
Under the dosage of the recrystallisation solvent and recrystallisation solvent, preferred crystallization temperature is 15~30 DEG C.
In the present invention, the cyclohexanone oxime vapour phase rearrangement product is contacted with the recrystallisation solvent, and 50 DEG C~
It is sufficiently dissolved at 73 DEG C.
Preferably, the temperature of dissolution is 58 DEG C~65 DEG C.
Preferably, desolventizing tower negative pressure is -60kpa~-80kpa, tower reactor in the crude caprolactam solvent removal step
At 100 DEG C~140 DEG C, tower top temperature is controlled at 70 DEG C~90 DEG C for temperature control.
Preferably, in caprolactam distilation steps after the desolventizing, destilling tower negative pressure be -90kpa~-
100kpa, at 150 DEG C~180 DEG C, tower top temperature is controlled at 100 DEG C~140 DEG C for bottom temperature control.
A kind of method of preferred purification cyclohexanone oxime vapour phase rearrangement product of the invention, comprising the following steps:
Step (1): cyclohexanone oxime is passed through into gas phase beckmann rearrangement, obtains rearrangement reaction liquid；By the rearrangement reaction liquid
Desolventizing, dehydration, de- light impurity, obtain the cyclohexanone oxime vapour phase rearrangement product；
Step (2): cyclohexanone oxime vapour phase rearrangement product to be refined is dissolved in recrystallisation solvent, through crystallization, solid after
Liquid separation, obtains crude caprolactam；Crude caprolactam obtains refined caprolactam through desolventizing, distillation；
At least one of the Di Iso Propyl Ether of the main solvent, hexamethylene, n-hexane, chlorocyclohexane；
The cosolvent is methanol and/or ethyl alcohol；
Cosolvent is the 3%~6% of the weight percent of main solvent；
The mass ratio of the cyclohexanone oxime vapour phase rearrangement product and recrystallisation solvent is 1~1.5: 1；
Crystallization temperature is 15~30 DEG C.
Preferably, step (2), the cyclohexanone oxime vapour phase rearrangement product is contacted with the recrystallisation solvent, and
It is sufficiently dissolved at 50 DEG C~73 DEG C.
Preferably, step (2), in the crude caprolactam solvent removal step, desolventizing tower negative pressure be -60kpa~-
80kpa, at 100 DEG C~140 DEG C, tower top temperature is controlled at 70 DEG C~90 DEG C for bottom temperature control.
Preferably, step (2), in the caprolactam distilation steps after the desolventizing, destilling tower negative pressure is -90kpa
~-100kpa, at 150 DEG C~180 DEG C, tower top temperature is controlled at 100 DEG C~140 DEG C for bottom temperature control.
Beneficial effect
The method of above-mentioned recycling cyclohexanone oxime vapour phase rearrangement product, by omitting weight-removing column, technique realization is not generated
The heavy raffinate of extra process is needed, process flow is simple, and waste water yield is low, low energy consumption, and low in the pollution of the environment, the rate of recovery is high, produces
Quality is good.
Studies have shown that the yield of the caprolactam after the method for the present invention purification is higher than 99%, quality meets caprolactam production
The national top grade product index (99.99%) of product.
Detailed description of the invention
Fig. 1 is the method flow diagram of purification cyclohexanone oxime vapour phase rearrangement product of the present invention.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing to the present invention
Specific embodiment be described in detail.Many details are explained in the following description in order to fully understand this hair
It is bright.But the invention can be embodied in many other ways as described herein, those skilled in the art can be not
Similar improvement is done in the case where violating intension of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
Referring to Fig. 1, the cyclohexanone oxime vapour phase rearrangement product purification method of an embodiment, comprising the following steps:
S110, desolventizing wait refine, dehydration, de- light impurity are provided after cyclohexanone oxime vapour phase rearrangement product.
Above-mentioned cyclohexanone oxime vapour phase rearrangement product liquid is obtained by following steps: cyclohexanone oxime is passed through gas phase Beckman weight
Row, obtains rearrangement reaction product；By above-mentioned rearrangement reaction product desolventizing, dehydration, de- light impurity, the cyclohexanone oxime gas is obtained
Phase rearrangement product.
S120, suitable solvent is added in the cyclohexanone oxime vapour phase rearrangement product；
Specifically, in the step of suitable recrystallisation solvent is added in the cyclohexanone oxime vapour phase rearrangement product, it is described heavy
The mass ratio of scheduled production object and recrystallisation solvent is 3: 1~1: 3, it is preferred that the mass ratio of above-mentioned rearrangement product and recrystallisation solvent is 1:
1。
Recrystallisation solvent includes main solvent and cosolvent.
Preferably, main solvent is propyl ether, butyl ether, Di Iso Propyl Ether, butyl ether, C6~C12Direct-connected alkane, C6~
C12Branched paraffin, C6~C12Cycloalkane, C6~C12Straight chain halogenated alkane, C6~C12Branch halogenated alkane or C6~C12
Halogenated cycloalkane.
It should be noted that butyl ether can be n-propyl n-butyl ether, n-propyl isobutyl ether, the tertiary fourth of n-propyl
Base ether, isopropyl n-butyl ether, isopropyl butyl ether or isopropyl tertbutyl ether.
Preferably, main solvent is Di Iso Propyl Ether, butyl ether etc..
It should be noted that in the main solvent that can be used, it is miscellaneous to increase added with appropriate alcohols (cosolvent)
Matter solubility.The alcohols includes methanol, ethyl alcohol, and additive amount is the 1%~15% of the main solvent weight ratio used, and preferably 3%
~8%.
It is appreciated that in other embodiments, solvent be not limited to it is listed above several, as long as can be molten by rearrangement product
Solution, achievees the purpose that crystal refining can be carried out.
Specifically, the solution temperature is 50 DEG C~73 DEG C in the step of sufficiently dissolving at a certain temperature, it is preferred that
The solution temperature is 58 DEG C~65 DEG C.
S130, above-mentioned solution is crystallized at 15 DEG C~60 DEG C, the caprolactam refined after centrifuge separation.
Specifically, above-mentioned solution is crystallized at 15 DEG C~60 DEG C, the step of the caprolactam refined after centrifuge separation
In, the mode of crystallization is selected from one-pot crystallisation by cooling, one-pot evaporative crystallization, continuous autoclave evaporative crystallization, OSLO crystallizer constant temperature knot
One of brilliant and OSLO crystallizer evaporative crystallization.
Above-mentioned solution is crystallized at 15 DEG C~60 DEG C, the step of the caprolactam refined after centrifuge separation in, centrifugation
The centrifuge used is separated as scraper type centrifuge, piston type centrifuge, helical conveyor centrifuge or centrifugal force type conveyer centrifugal.
Preferably, centrifuge is scraper type centrifuge.The revolving speed of centrifuge is 1000r/min~3000r/min.
It is appreciated that in step s 130, the caprolactam in solution is crystallized at 15 DEG C~60 DEG C, and is dissolved in the miscellaneous of solvent
Matter still dissolve in a solvent, by centrifuge separation, the caprolactam of crystallization and solution are separated, obtain primary purification oneself in
Amide.
In step s 130, the impure solvent after centrifuge separation can be re-used for dissolving after solvent recovery removing impurities
Rearrangement product.
S140, above-mentioned crude caprolactam desolventizing
Specifically, desolventizing tower negative pressure is -60kpa~-80kpa, tower reactor in the crude caprolactam solvent removal step
At 100 DEG C~140 DEG C, tower top temperature is controlled at 70 DEG C~90 DEG C for temperature control.
In step S140, desolventizing recovered solvent can be re-used for dissolution rearrangement product, reduce the discharge of waste liquid,
Reduce energy consumption.
Crude caprolactam distillation after S150, above-mentioned desolventizing
Specifically, in the caprolactam distilation steps after the desolventizing, destilling tower negative pressure be -90kpa~-
100kpa, at 150 DEG C~180 DEG C, tower top temperature is controlled at 100 DEG C~140 DEG C for bottom temperature control.
The method of above-mentioned recycling cyclohexanone oxime vapour phase rearrangement product, by omitting weight-removing column, technique realization is not generated
The heavy raffinate of extra process is needed, process flow is simple, and waste water yield is low, low energy consumption, and low in the pollution of the environment, the rate of recovery is high, produces
Quality is good.
Existing method can be used in the acquisition of cyclohexanone oxime vapour phase rearrangement product of the invention: for example, obtaining by the following method
:
Cyclohexanone oxime and methanol premixing, enter the fixed bed for being filled with solid acid catalyst, 300~500 after gasification
Reaction generates the multi-component material containing caprolactam at a temperature of DEG C.It is molten to become the methanol containing caprolactam after the substance is cooling
Liquid removes methanol by eparating methanol tower, using the water in dehydrating tower removal reaction product, sloughs in product using lightness-removing column
Lighter component, obtain the required crystallization raw material (cyclohexanone oxime vapour phase rearrangement product to be refined) of the present invention.
Embodiment and comparative example below are carried out using the cyclohexanone oxime vapour phase rearrangement product to be refined, specifically
It is as follows:
Embodiment 1
Cyclohexanone oxime vapour phase rearrangement product to be refined is provided, it is different that two are added in above-mentioned cyclohexanone oxime vapour phase rearrangement product
The methanol of propyl ether and Di Iso Propyl Ether quality 6%, rearrangement product and total solvent mass ratio are 1.5: 1, at 67 DEG C sufficiently
Then dissolution crystallizes at 15 DEG C, the caprolactam of primary purification is obtained after centrifuge separation.Slightly oneself desolventizing tower negative pressure be-
80kpa, 100 DEG C of bottom temperature, desolventizing under the operating condition that 70 DEG C of tower top temperature；Caprolactam after desolventizing is distilling
Tower -99.8kpa, 154 DEG C of bottom temperature, tower top temperature control is distilled under 130 DEG C of operating condition, is finally produced
Product, the caprolactam rate of recovery 99%.The purity for recycling obtained caprolactam is greater than 99.99%.
Embodiment 2
Cyclohexanone oxime vapour phase rearrangement product to be refined is provided, it is different that two are added in above-mentioned cyclohexanone oxime vapour phase rearrangement product
The methanol of propyl ether and Di Iso Propyl Ether quality 6%, rearrangement product and total solvent mass ratio are 1: 1.5, at 67 DEG C sufficiently
Then dissolution crystallizes at 15 DEG C, the caprolactam of primary purification is obtained after centrifuge separation.Slightly oneself desolventizing tower negative pressure be-
80kpa, 100 DEG C of bottom temperature, desolventizing under the operating condition that 70 DEG C of tower top temperature；Caprolactam after desolventizing is distilling
Tower -99.8kpa, 154 DEG C of bottom temperature, tower top temperature control is distilled under 130 DEG C of operating condition, is finally produced
Product, the caprolactam rate of recovery 83%.The purity for recycling obtained caprolactam is greater than 99.99%.It compares, improves with embodiment 1
The ratio of recrystallisation solvent, product purity remains to reach national top grade level, but product yield is slightly decreased.
Comparative example 1
Cyclohexanone oxime vapour phase rearrangement product to be refined is provided, the matter such as addition in above-mentioned cyclohexanone oxime vapour phase rearrangement product
Measure ratio Di Iso Propyl Ether, sufficiently dissolved at 60 DEG C, then 15 DEG C crystallize, obtained after centrifuge separation primary purification oneself in
Amide.Slightly oneself is -60kpa in desolventizing tower negative pressure, 120 DEG C of bottom temperature, desolventizing under the operating condition that 81 DEG C of tower top temperature；
Caprolactam after desolventizing is in destilling tower -100kpa, and 150 DEG C of bottom temperature, tower top temperature controls the operating condition at 110 DEG C
Under distilled, obtain final products, the caprolactam rate of recovery 96%.Recycle the purity situation purity of obtained caprolactam
98.97%.It is compared with embodiment 1, using single solvent, the purity and yield of product are decreased obviously.
Comparative example 2
Cyclohexanone oxime vapour phase rearrangement product to be refined is provided, it is different that two are added in above-mentioned cyclohexanone oxime vapour phase rearrangement product
The methanol of propyl ether and Di Iso Propyl Ether quality 16%, rearrangement product and total solvent mass ratio are 1.5: 1, at 67 DEG C sufficiently
Then dissolution crystallizes at 15 DEG C, the caprolactam of primary purification is obtained after centrifuge separation.Slightly oneself desolventizing tower negative pressure be-
80kpa, 100 DEG C of bottom temperature, desolventizing under the operating condition that 70 DEG C of tower top temperature；Caprolactam after desolventizing is distilling
Tower -99.8kpa, 154 DEG C of bottom temperature, tower top temperature control is distilled under 130 DEG C of operating condition, is finally produced
Product, the caprolactam rate of recovery 43%.The purity for recycling obtained caprolactam is greater than 99.99%.It compares, improves with embodiment 1
The yield of the ratio of the cosolvent of recrystallisation solvent, product is decreased obviously.
Comparative example 3
Cyclohexanone oxime vapour phase rearrangement product to be refined is provided, it is different that two are added in above-mentioned cyclohexanone oxime vapour phase rearrangement product
The propyl alcohol of propyl ether and Di Iso Propyl Ether quality 6%, rearrangement product and total solvent mass ratio are 1.5: 1, at 67 DEG C sufficiently
Then dissolution crystallizes at 15 DEG C, the caprolactam of primary purification is obtained after centrifuge separation.Slightly oneself desolventizing tower negative pressure be-
80kpa, 100 DEG C of bottom temperature, desolventizing under the operating condition that 70 DEG C of tower top temperature；Caprolactam after desolventizing is distilling
Tower -99.8kpa, 154 DEG C of bottom temperature, tower top temperature control is distilled under 130 DEG C of operating condition, is finally produced
Product, the caprolactam rate of recovery 99%.Recycle the purity 99.18% of obtained caprolactam.It is compared with embodiment 1, propyl alcohol conduct
When crystallizing cosolvent, product purity is substantially reduced.
Comparative example 4
Cyclohexanone oxime vapour phase rearrangement product to be refined is provided, it is different that two are added in above-mentioned cyclohexanone oxime vapour phase rearrangement product
The butanol of propyl ether and Di Iso Propyl Ether quality 6%, rearrangement product and total solvent mass ratio are 1.5: 1, at 67 DEG C sufficiently
Then dissolution crystallizes at 15 DEG C, the caprolactam of primary purification is obtained after centrifuge separation.Slightly oneself desolventizing tower negative pressure be-
80kpa, 100 DEG C of bottom temperature, desolventizing under the operating condition that 70 DEG C of tower top temperature；Caprolactam after desolventizing is distilling
Tower -99.8kpa, 154 DEG C of bottom temperature, tower top temperature control is distilled under 130 DEG C of operating condition, is finally produced
Product, the caprolactam rate of recovery 99%.Recycle the purity 98.86% of obtained caprolactam.It is compared with embodiment 1, butanol conduct
When crystallizing cosolvent, product purity is substantially reduced.
Embodiment 3
Cyclohexanone oxime vapour phase rearrangement product to be refined is provided, it is different that two are added in above-mentioned cyclohexanone oxime vapour phase rearrangement product
The methanol of propyl ether and Di Iso Propyl Ether quality 0.5%, rearrangement product and total solvent mass ratio are 1.5: 1, are filled at 67 DEG C
Divide dissolution, is then crystallized at 15 DEG C, the caprolactam of primary purification is obtained after centrifuge separation.Slightly oneself desolventizing tower negative pressure be-
80kpa, 100 DEG C of bottom temperature, desolventizing under the operating condition that 70 DEG C of tower top temperature；Caprolactam after desolventizing is distilling
Tower -99.8kpa, 154 DEG C of bottom temperature, tower top temperature control is distilled under 130 DEG C of operating condition, is finally produced
Product, the caprolactam rate of recovery 99%.Recycle the purity 99.91% of obtained caprolactam.It is compared with comparative example 2, in main solvent
The middle micro cosolvent of addition, can be in the case where guaranteeing product purity, hence it is evident that promote the yield of product.
Comparative example 5
Cyclohexanone oxime vapour phase rearrangement product to be refined is provided, hexamethylene is added in above-mentioned cyclohexanone oxime vapour phase rearrangement product
Alkane, rearrangement product and hexamethylene mass ratio are 1: 2, are sufficiently dissolved at 63 DEG C, then crystallize at 30 DEG C, obtain after centrifuge separation
The caprolactam of primary purification.Slightly oneself desolventizing tower negative pressure be -70kpa, 110 DEG C of bottom temperature, the behaviour that 75 DEG C of tower top temperature
Desolventizing under the conditions of work；Caprolactam after desolventizing is in destilling tower -99.5kpa, and 160 DEG C of bottom temperature, tower top temperature controls
It is distilled under 120 DEG C of operating condition, obtains final products, the caprolactam rate of recovery 93%.Recycle obtain oneself in acyl
The purity situation 99.89% of amine.Using single solvent, the purity and yield of product decline to a certain degree.
Embodiment 4
Cyclohexanone oxime vapour phase rearrangement product to be refined is provided, hexamethylene is added in above-mentioned cyclohexanone oxime vapour phase rearrangement product
The ethyl alcohol of alkane and hexamethylene quality 4%, rearrangement product and hexamethylene mass ratio are 1: 2, sufficiently dissolve at 63 DEG C, then exist
30 DEG C of crystallizations, obtain the caprolactam of primary purification after centrifuge separation.Slightly oneself is -70kpa, bottom temperature in desolventizing tower negative pressure
110 DEG C, desolventizing under the operating condition that 75 DEG C of tower top temperature；Caprolactam after desolventizing is in destilling tower -99.5kpa, tower reactor
160 DEG C of temperature, tower top temperature control is distilled under 120 DEG C of operating condition, obtains final products, the caprolactam rate of recovery
82%.The purity for recycling obtained caprolactam is greater than 99.99%.It is compared with comparative example 5, certain second is added in main solvent
Alcohol helps that the purity of product is made to reach national top grade level, but crystallization total solvent usage amount is larger, and the yield of product is not very
It is ideal.
Comparative example 6
Cyclohexanone oxime vapour phase rearrangement product to be refined is provided, be added in above-mentioned cyclohexanone oxime vapour phase rearrangement product just oneself
Alkane, rearrangement product and total solvent mass ratio are 1.5: 1, are sufficiently dissolved at 70 DEG C, are then crystallized at 15 DEG C, after centrifuge separation
To the caprolactam of primary purification.Slightly oneself desolventizing tower negative pressure be -80kpa, 100 DEG C of bottom temperature, 70 DEG C of tower top temperature
Desolventizing under operating condition；Caprolactam after desolventizing is in destilling tower -99.8kpa, and 154 DEG C of bottom temperature, tower top temperature control
System is distilled under 130 DEG C of operating condition, obtains final products, the caprolactam rate of recovery 99%.Recycle obtain oneself in
The purity 96.63% of amide.Using single solvent, the purity decline of product is obvious.
Embodiment 5
Cyclohexanone oxime vapour phase rearrangement product to be refined is provided, be added in above-mentioned cyclohexanone oxime vapour phase rearrangement product just oneself
The ethyl alcohol of alkane and n-hexane quality 3%, rearrangement product and total solvent mass ratio are 1.5: 1, are sufficiently dissolved at 67 DEG C, then
It is crystallized at 15 DEG C, the caprolactam of primary purification is obtained after centrifuge separation.Slightly oneself is -80kpa, tower reactor temperature in desolventizing tower negative pressure
100 DEG C are spent, desolventizing under the operating condition that 70 DEG C of tower top temperature；Caprolactam after desolventizing is in destilling tower -99.8kpa, tower
154 DEG C of kettle temperature degree, tower top temperature control is distilled under 130 DEG C of operating condition, obtains final products, caprolactam recycling
Rate 99%.The purity for recycling obtained caprolactam is greater than 99.99%.It is compared with embodiment 3, appropriate second is added in n-hexane
Alcohol, and the usage amount of recrystallisation solvent is controlled, facilitate the yield for being obviously improved product.
Comparative example 7
Cyclohexanone oxime vapour phase rearrangement product to be refined is provided, chloro is added in above-mentioned cyclohexanone oxime vapour phase rearrangement product
Hexamethylene, resetting with chlorocyclohexane mass ratio is 1: 3, sufficiently dissolves, then crystallizes at 40 DEG C, after centrifuge separation at 70 DEG C
Obtain the caprolactam of primary purification.Slightly oneself desolventizing tower negative pressure be -77kpa, 105 DEG C of bottom temperature, 73 DEG C of tower top temperature
Operating condition under desolventizing；Caprolactam after desolventizing is in destilling tower -100kpa, and 150 DEG C of bottom temperature, tower top temperature control
System is distilled under 123 DEG C of operating condition, obtains final products, the caprolactam rate of recovery 91%.Recycle obtain oneself in
The purity situation 99.93% of amide.Using single chlorocyclohexane, the yield and purity of product are undesirable, and recrystallisation solvent
Usage amount is big.
Embodiment 6
Cyclohexanone oxime vapour phase rearrangement product to be refined is provided, chloro is added in above-mentioned cyclohexanone oxime vapour phase rearrangement product
The ethyl alcohol of hexamethylene and chlorocyclohexane quality 5%, rearrangement product and chlorocyclohexane mass ratio are 1: 3, are filled at 70 DEG C
Divide dissolution, is then crystallized at 40 DEG C, the caprolactam of primary purification is obtained after centrifuge separation.Slightly oneself desolventizing tower negative pressure be-
77kpa, 105 DEG C of bottom temperature, desolventizing under the operating condition that 73 DEG C of tower top temperature；Caprolactam after desolventizing is distilling
Tower -100kpa, 150 DEG C of bottom temperature, tower top temperature control is distilled under 123 DEG C of operating condition, obtains final products,
The caprolactam rate of recovery 76%.The purity for recycling obtained caprolactam is greater than 99.99%.It is compared with comparative example 7, addition is certain
Ethyl alcohol as recrystallisation solvent, it is horizontal that the purity of product may conform to national top grade, but recrystallisation solvent capacity increases, the yield of product
It is undesirable.
Embodiment 7
Cyclohexanone oxime vapour phase rearrangement product to be refined is provided, chloro is added in above-mentioned cyclohexanone oxime vapour phase rearrangement product
The ethyl alcohol of hexamethylene and chlorocyclohexane quality 5%, rearrangement product and chlorocyclohexane mass ratio are 4: 1, are filled at 70 DEG C
Divide dissolution, is then crystallized at 40 DEG C, the caprolactam of primary purification is obtained after centrifuge separation, in the process magma difficulty of transportation.Slightly
Oneself is -77kpa in desolventizing tower negative pressure, 105 DEG C of bottom temperature, desolventizing under the operating condition that 73 DEG C of tower top temperature；Desolventizing
Caprolactam afterwards is in destilling tower -100kpa, and 150 DEG C of bottom temperature, tower top temperature control carries out under 123 DEG C of operating condition
Distillation, obtains final products, the caprolactam rate of recovery 99%.Recycle the purity 99.87% of obtained caprolactam.
To sum up, in method for crystallising of the invention, not to vapour phase rearrangement product carry out it is de- handle again in the case where, by
Certain methanol or ethyl alcohol are added in recrystallisation solvent, the purity of product can reach national top grade, further control recrystallisation solvent
Usage amount, can further promote the yield of product.Studies have shown that under preferred scheme, such as embodiment 1 and 5；Described
Cosolvent is methanol and/or ethyl alcohol, and cosolvent is the 0.5%~8% of main solvent quality content；The cyclohexanone oxime vapour phase rearrangement
Under the collaboration that product is 1~1.5: 1 with the mass ratio of recrystallisation solvent, the purity of product is better than national top grade standard comprehensively
(99.99%)；Yield is also above 99%.Compared to the prior art, with the obvious advantage.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (20)
1. a kind of method for refining cyclohexanone oxime vapour phase rearrangement product, which is characterized in that by cyclohexanone oxime gas phase weight to be refined
Scheduled production object is dissolved in recrystallisation solvent, through crystallization, separation of solid and liquid after, obtains crude caprolactam；Crude caprolactam is through desolventizing, steaming
It evaporates, obtains refined caprolactam；
The recrystallisation solvent includes main solvent and cosolvent；The main solvent is ether, hydro carbons, at least one in halogenated hydrocarbons
Kind；
The cosolvent is alcohol.
2. the method for purification cyclohexanone oxime vapour phase rearrangement product as described in claim 1, which is characterized in that the cyclohexanone oxime
Vapour phase rearrangement product is obtained by following steps:
Cyclohexanone oxime is passed through into gas phase beckmann rearrangement, obtains rearrangement reaction liquid；And
By the rearrangement reaction liquid desolventizing, dehydration, de- light impurity, the cyclohexanone oxime vapour phase rearrangement product is obtained.
3. the method for purification cyclohexanone oxime vapour phase rearrangement product as claimed in claim 1 or 2, which is characterized in that the master
The boiling range of solvent is lower than 270 DEG C.
4. the method for purification cyclohexanone oxime vapour phase rearrangement product as claimed in claim 3, which is characterized in that the solvent is third
Ether, butyl ether, Di Iso Propyl Ether, butyl ether, C6~C12Direct-connected alkane, C6~C12Branched paraffin, C6~C12Cycloalkanes
Hydrocarbon, C6~C12Straight chain halogenated alkane, C6~C12Branch halogenated alkane or C6~C12Halogenated cycloalkane and its mixture.
5. the method for purification cyclohexanone oxime vapour phase rearrangement product as claimed in claim 4, which is characterized in that the main solvent
Boiling range be 68~142 DEG C.
6. the method for purification cyclohexanone oxime vapour phase rearrangement product as claimed in claim 5, which is characterized in that the main solvent
Di Iso Propyl Ether, hexamethylene, n-hexane, at least one of chlorocyclohexane.
7. the method for purification cyclohexanone oxime vapour phase rearrangement product as claimed in claim 3, which is characterized in that the cosolvent
Boiling range be lower than 100 DEG C.
8. the method for purification cyclohexanone oxime vapour phase rearrangement product as claimed in claim 7, which is characterized in that the cosolvent
Boiling range be 40~80 DEG C.
9. the method for purification cyclohexanone oxime vapour phase rearrangement product as claimed in claim 8, which is characterized in that the cosolvent
For methanol and/or ethyl alcohol.
10. the method for purification cyclohexanone oxime vapour phase rearrangement product as described in any one of claims 1 to 9, which is characterized in that help
Solvent is the 0.1%~15% of main solvent weight percent.
11. the method for purification cyclohexanone oxime vapour phase rearrangement product as claimed in claim 10, which is characterized in that based on cosolvent
The 0.5%~8% of the weight percent of solvent.
12. the method for purification cyclohexanone oxime vapour phase rearrangement product as claimed in claim 10, which is characterized in that based on cosolvent
The 3%~6% of the weight percent of solvent.
13. the method for purification cyclohexanone oxime vapour phase rearrangement product as claimed in claim 10, which is characterized in that the cyclohexanone
The mass ratio of oxime vapour phase rearrangement product and recrystallisation solvent is 4: 1~1: 3.
14. the method for purification cyclohexanone oxime vapour phase rearrangement product as claimed in claim 13, which is characterized in that the cyclohexanone
The mass ratio of oxime vapour phase rearrangement product and recrystallisation solvent is 1~1.5: 1.
15. the method for purification cyclohexanone oxime vapour phase rearrangement product as claimed in claim 13, which is characterized in that crystallization temperature is
15~60 DEG C.
16. the method for purification cyclohexanone oxime vapour phase rearrangement product as claimed in claim 15, which is characterized in that crystallization temperature is
15~30 DEG C.
17. the method for purification cyclohexanone oxime vapour phase rearrangement product as described in claim 1, which is characterized in that by the ring
Hexanone oxime vapour phase rearrangement product is contacted with the recrystallisation solvent, and is sufficiently dissolved at 50 DEG C~73 DEG C.
18. the method for purification cyclohexanone oxime vapour phase rearrangement product as claimed in claim 17, which is characterized in that the temperature of dissolution
It is 58 DEG C~65 DEG C.
19. the method for purification cyclohexanone oxime vapour phase rearrangement product as described in claim 1, which is characterized in that described thick in oneself
In amide solvent removal step, desolventizing tower negative pressure is -60kpa~-80kpa, and bottom temperature control is at 100 DEG C~140 DEG C, tower top
Temperature is controlled at 70 DEG C~90 DEG C.
20. the method for purification cyclohexanone oxime vapour phase rearrangement product as described in claim 1, which is characterized in that the desolventizing
In caprolactam distilation steps afterwards, destilling tower negative pressure is -90kpa~-100kpa, and bottom temperature is controlled 150 DEG C~180
DEG C, tower top temperature is controlled at 100 DEG C~140 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142670A (en) * | 2020-09-02 | 2020-12-29 | 浙江恒澜科技有限公司 | Preparation method of caprolactam |
| CN112159357A (en) * | 2020-10-15 | 2021-01-01 | 浙江恒澜科技有限公司 | Refining method of caprolactam |
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| CN104011017A (en) * | 2011-12-28 | 2014-08-27 | 住友化学株式会社 | Process for producing epsilon-caprolactam |
| CN104024221A (en) * | 2011-12-28 | 2014-09-03 | 住友化学株式会社 | Method for producing high-quality epsilon-caprolactam |
| CN106146374A (en) * | 2015-04-02 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of method recycling cyclohexanone-oxime vapour phase rearrangement product fractionation weight residual liquid |
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| US3839324A (en) * | 1970-12-22 | 1974-10-01 | Inventa Ag | Process for the purification of caprolactam |
| CN1332158A (en) * | 2000-06-27 | 2002-01-23 | 住友化学工业株式会社 | Prep. of epsilon-hexanolactam |
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| CN112159357A (en) * | 2020-10-15 | 2021-01-01 | 浙江恒澜科技有限公司 | Refining method of caprolactam |
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