CN102875468A - Method for producing caprolactam through gas phase rearrangement of cyclohexanone-oxime - Google Patents
Method for producing caprolactam through gas phase rearrangement of cyclohexanone-oxime Download PDFInfo
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Abstract
A method for producing caprolactam through the gas phase rearrangement of cyclohexanone-oxime comprises a process of separating and recovering caprolactam from a crude caprolactam product and an application of the process in the preparation method of caprolactam. The method comprises the following steps: removing water and light byproducts from the crude caprolactam product, allowing the water and light byproducts removed crude caprolactam product to enter a weight removing tower, fractioning and removing heavy byproducts under an absolute pressure of 0-0.5bar at a tower bottom temperature of 100-200DEG C to obtain a caprolactam product at the tower top and caprolactam-containing heavy byproducts at the tower bottom, introducing the caprolactam-containing heavy byproducts into a forced evaporation unit, evaporating out caprolactam at a low temperature, condensing the obtained evaporated gas phase, returning the condensed gas phase to the weight removing tower, and discharging a residual liquid phase which is obtained after the evaporation and is heavy byproducts from the unit. The method provided by the invention improves the caprolactam yield and simultaneously reduces the amount of three wastes.
Description
Technical field
The present invention relates to a kind of cyclohexanone-oxime and produce the method for hexanolactam, more particularly, relate to the method that hexanolactam is produced in a kind of cyclohexanone-oxime vapor phase rearrangement.
Technical background
ε-caprolactam (being designated hereinafter simply as hexanolactam) is the main raw material of producing polyamide fibre, industrial cord thread and nylon engineering plastic three large series product, and along with the continuous increase of domestic project plastics demand, its demand also is the trend that increases year by year.Domestic apparent demand amount was 90.1 ten thousand tons in 2009, and actual import volume is 600,000 tons.As seen, the breach of domestic hexanolactam is quite huge.Along with the continuous increase of nylon engineering plastic consumption, the state of the unbalanced supply-demand of domestic hexanolactam will manifest more.
The industrial cyclohexanone-oxime liquid phase Beckmann rearrangement explained hereafter hexanolactam that adopts take the vitriol oil or oleum as catalyzer more.Adopt the hexanolactam of this explained hereafter to account for about 90% of world's caprolactam production total amount.Although this processing method reaches 98.5% to the selectivity of hexanolactam, its maximum shortcoming is: 1 ton of hexanolactam of every production will producing ammonium sulfate byproduct 1.3-1.8 ton.Use in addition the vitriol oil or oleum can cause equipment corrosion and environmental pollution, this has produced contradiction with the chemical background of advocating Atom economy and environmental protection and economy.
In order to satisfy industrial production and environmental requirement, the cyclohexanone-oxime gas phase beckmann rearrangement technique take solid acid as catalyzer is expected to replace liquid phase rearrangement technique.It does not consume oleum and ammonia in the rearrangement reaction process, have without equipment corrosion, non-environmental-pollution and the advantage such as producing ammonium sulfate byproduct not.
Rearrangement of cyclohexanone-oxime is produced in the reaction of hexanolactam except generating hexanolactam, also generates the polymer by product of minute quantity.Liquid phase rearrangement technique, its weight byproduct stream all turn back to the rearrangement reactor recycling, and the part by product contacts with catalyzer can regenerate hexanolactam, so the yield of the treating process hexanolactam of rearrangement reaction can reach more than 99.5%.And the heavier by product of the minute quantity that generates in the vapor phase rearrangement process reactor is discharged no longer Returning reactor recycling behind the reactor with the product hexanolactam.Secondly, also produce a small amount of polymer in the rectifying of solvent recovery tower separation solvent, the heavier side components that these boiling points are higher finally accumulates in the weight-removing column tower reactor.The content that the tower reactor restructuring divides is more, and the tower reactor temperature is also higher.In addition, because hexanolactam thermo-sensitivity, distillation temperature generally should not surpass 200 ℃, so still contain the hexanolactam about 60wt% in the material that tower reactor is discharged.So in rectifying, need to lose a part of hexanolactam to guarantee the tower reactor temperature, this just causes the hexanolactam yield of vapor phase rearrangement technique to only have about 96%, hexanolactam has reduced the yield of hexanolactam with the loss of heavy product, increase the burden that the three wastes are processed, affected the economic benefit of vapor phase rearrangement device.With respect to the liquid phase technique of retaking, gap is apparent in view, and therefore for improving competitive power and the economic benefit of vapor phase rearrangement technique, it is very necessary improving vapor phase rearrangement technique hexanolactam yield.
Summary of the invention
The thick product separation of hexanolactam that one of the technical problem to be solved in the present invention provides a kind of yield that can the Effective Raise hexanolactam reclaims the method for hexanolactam.
Two of the technical problem to be solved in the present invention provides the method that hexanolactam is produced in the higher cyclohexanone-oxime vapor phase rearrangement of a kind of product yield.
The thick product separation of a kind of hexanolactam provided by the invention reclaims the method for hexanolactam, comprise: the thick product of the hexanolactam behind the desolventizing is through dehydration, after taking off light by-product, enter that fractionation removes heavier by product in the weight-removing column, weight-removing column is 0-0.5bar in absolute pressure, the tower reactor temperature is to operate under 100-200 ℃ the condition, cat head obtains caprolactam product, the tower reactor discharging is the heavier by product that contains hexanolactam, the forced evaporation unit is introduced in discharging at the bottom of the tower, at a lower temperature hexanolactam is evaporated, gas phase after the evaporation is returned after condensation in the weight-removing column, and the residual liquid phase after the evaporation is heavier by product discharger.
In the method for recovery hexanolactam provided by the invention, the preferred luwa evaporator in described forced evaporation unit, 130-170 ℃ than under the low operating temperature, hexanolactam is evaporated.
The beneficial effect that the thick product separation of hexanolactam provided by the invention reclaims the method for hexanolactam is:
Method provided by the invention increases the forced evaporation unit and further reclaims hexanolactam in conventional Separation and Recovery flow process, and high boiling heavy product component is in time discharged system.Improve the yield of hexanolactam, reduced simultaneously the amount of device effluent discharge.Can be applied to vapor phase process and liquid phase method and produce the technological process of hexanolactam.
The method of hexanolactam is produced in cyclohexanone-oxime vapor phase rearrangement provided by the invention, comprise cyclohexanone-oxime and high-temperature solvent and carrier gas mixing gasifying, introduce in the rearrangement reactor with the gas phase form, filling solid acid catalyst in the rearrangement reactor, cyclohexanone-oxime contacts with solid acid catalyst, it is 200-500 ℃ in temperature, absolute pressure is that reaction generates hexanolactam under the condition of 2.1-26bar, reacted logistics gas-liquid separation after the heat exchange cooling, isolated liquid phase is introduced the thick product of hexanolactam after solvent recovery tower is separated into solvent and desolventizing, the thick product of hexanolactam behind the desolventizing is through dehydration, after taking off light by-product, enter that fractionation removes heavier by product in the weight-removing column, weight-removing column is 0-0.5bar in absolute pressure, the tower reactor temperature is to operate under 100-200 ℃ the condition, cat head obtains caprolactam product, the forced evaporation unit is introduced in the tower reactor discharging, in absolute pressure less than 0.1bar, temperature is to operate under 130-170 ℃ the condition, gas phase after the evaporation is returned after condensation in the weight-removing column, and the residual liquid phase after the evaporation is the by product discharger.
The beneficial effect that the method for hexanolactam is produced in cyclohexanone-oxime vapor phase rearrangement provided by the invention is:
The method that hexanolactam is produced in cyclohexanone-oxime vapor phase rearrangement provided by the invention increases the forced evaporation unit in the flow process of follow-up thick product separation recovery hexanolactam, than under the low operating temperature, hexanolactam is evaporated, and high boiling heavy product component is in time discharged system.Improve the yield of hexanolactam, reduced simultaneously the amount of the three wastes.
Description of drawings
Fig. 1 is the schematic flow sheet that the thick product separation of hexanolactam provided by the invention reclaims the hexanolactam method;
Fig. 2 is the method flow synoptic diagram of cyclohexanone-oxime vapor phase rearrangement provided by the invention hexanolactam processed;
Fig. 3 is the schematic flow sheet that the thick product separation of hexanolactam reclaims the hexanolactam method in the Comparative Examples;
Wherein: 1, dehydration tower, 2, lightness-removing column, 3, weight-removing column, 4, luwa evaporator, 5, condenser, 6, the reaction product interchanger, 7, knockout drum, 8, solvent recovery tower, 9, process furnace, 10, rearrangement reactor.
Embodiment
Cyclohexanone-oxime Beckmann rearrangement product separation provided by the invention reclaims the method for hexanolactam, is such implementation:
Cyclohexanone-oxime Beckmann rearrangement product behind the desolventizing be the thick product introduction dehydration tower of hexanolactam remove in the reaction product with water, dehydration tower operation absolute pressure is 0-0.5bar, the tower reactor temperature is 100-180 ℃, the dehydration column overhead discharging is water, the tower reactor discharging enters lightness-removing column, be 0-0.5bar in absolute pressure, remove wherein lighter by product under 100-200 ℃ of the tower reactor temperature, the discharging of lightness-removing column cat head is light by-product, the tower reactor discharging enters weight-removing column and removes heavier by product, be 0-0.5bar in absolute pressure, under the condition that the tower reactor temperature is 100-200 ℃, the weight-removing column cat head obtains caprolactam product, the tower reactor discharging is the heavier by product that contains hexanolactam, the forced evaporation unit is introduced in discharging at the bottom of the tower, under lower temperature, hexanolactam is evaporated, gas phase after the evaporation reclaims through condensation and returns in the weight-removing column, and the residual liquid phase after the evaporation is heavier by product discharger.
In the method provided by the invention, described forced evaporation unit is the higher equipment of vaporization efficiency, is preferably luwa evaporator, and described luwa evaporator is a kind of by rotor segment pressure film forming, the vaporizer that can carry out falling film evaporation under vacuum condition.Its heat transfer coefficient is large, evaporation capacity is high, the overcurrent time short, especially is fit to evaporation concentration, the distilation that heat-sensitive material, high-viscosity material and easy crystallization contain granule materials; Mainly formed by motor, speed reduction unit, separator cartridge, distributor, gas-liquid separator, evaporation stack shell, rotor, scraper plate etc.
In the method provided by the invention, adopt luwa evaporator as the forced evaporation unit, equipment volume is less, and the expense of relating operation is lower.It is 130-170 ℃ less than 0.1bar, temperature that the operational condition of luwa evaporator is preferably absolute pressure.
The embodiment that the method for hexanolactam is produced in cyclohexanone-oxime vapor phase rearrangement provided by the invention is:
With cyclohexanone-oxime and high-temperature solvent and carrier gas mixing gasifying, introduce in the reactor with the gas phase form, cyclohexanone-oxime contacts with solid acid catalyst, it is 200-500 ℃ in temperature, pressure is that reaction generates hexanolactam under the condition of 2.1-26bar, reacted logistics is introduced in the knockout drum after heat exchange, be 1-5bar in absolute pressure, temperature is under 20-90 ℃ the condition, through one or more levels gas-liquid separation, isolated gas phase is carrier gas, isolated liquid phase is reaction product and solvent, and liquid phase enters the reaction product after solvent recovery tower further is separated into solvent and desolventizing, the reaction product behind the desolventizing enter dehydration tower remove in the reaction product with water, the dehydration tower operational condition is: absolute pressure is 0-0.5bar, and the tower reactor temperature is 100-180 ℃.Reaction product after the dehydration is introduced lightness-removing column, at absolute pressure 0-0.5bar, under the condition that the tower reactor temperature is 100-200 ℃, the cat head discharging is light by-product, the tower reactor discharging is the reaction product after taking off gently, enter again weight-removing column and remove heavier by product, the operational condition of weight-removing column is: absolute pressure is 0-0.5bar, the tower reactor temperature is 100-200 ℃, the weight-removing column cat head obtains caprolactam product, the tower reactor discharging is heavier by product, wherein also contain the above hexanolactam of 60wt%, the forced evaporation unit is introduced in the tower reactor discharging, less than absolute pressure 0.1, temperature is to operate under 130-170 ℃ the condition, gas phase after the evaporation reclaims through condensation and returns in the weight-removing column, and the residual liquid phase after the evaporation is the by product discharger.
In the method provided by the invention, after heat exchange, introduce in the knockout drum by logistics after out the reaction in the rearrangement reactor, be 1-5bar in absolute pressure, temperature is to be separated into gas-liquid two-phase under 20-90 ℃ the condition, can be in the one-level knockout drum, to be separated into gas-liquid two-phase, also can be separated into gas-liquid two-phase through two-stage or multi-stage gas-liquid separating tank.
In the method provided by the invention, preferred flow process is to introduce the flash trapping stage tank after heat exchange by logistics after out the reaction in the rearrangement reactor, be 1-5bar in absolute pressure, temperature is to be separated into gas-liquid two-phase under 60-90 ℃ the condition, and isolated liquid phase is introduced the thick product of hexanolactam that is separated in the solvent recovery tower behind solvent and the desolventizing; The isolated gas phase of flash trapping stage tank is introduced in the second-order separation tank, is separated into gas-liquid two-phase under 20-40 ℃ condition, and wherein liquid phase is returned recycle in the rearrangement reactor after the liquor pump pressurization; Isolated gas phase is mainly carrier gas, returns rearrangement reactor and recycle after the gas compressor pressurization.
This preferred flow is separated rearrangement of cyclohexanone-oxime reaction product two-stage gas-liquid two-phase under different potential temperatures, the isolated liquid phase of high potential temperature is mainly the reaction product that contains a small amount of solvent, and then the introducing solvent recovery tower, reduced treatment capacity and the energy consumption of solvent recovery tower.Low-temperature level separates the liquid phase that obtains and is mainly solvent, can directly return the rearrangement reactor recycle.Simultaneously, the amount that low-temperature level separates the gas phase that obtains also reduces, and therefore solvent composition content wherein seldom reduced the gas volume that gas compressor is carried, and reduced the energy consumption of gas compressor.
In the method provided by the invention, described solid acid catalyst is the catalyzer that contains HTS, silica zeolite or have the MFI structure molecular screen, preferably contains the molecular sieve with MFI structure, more preferably the ZSM-5 molecular sieve of silicon/aluminum ratio 〉=500.
In the method provided by the invention, described solvent is selected from C1-C6 Fatty Alcohol(C12-C14 and C12-C18) or their mixture, the mixture of one or more in particular methanol, ethanol and the propyl alcohol.The weight ratio of described solvent and cyclohexanone-oxime is at (10-80): (90-20).
In the method provided by the invention, described inert carrier gas is selected from nitrogen, hydrogen, argon gas, ammonia and boiling point and is not higher than 180 ℃ stable hydrocarbon and one or more the mixture in the halohydrocarbon.The mol ratio of described carrier gas and cyclohexanone-oxime is at (5-100): 1
In the method provided by the invention, the temperature of logistics is 250-550 ℃ after the reaction that described vapor phase rearrangement reactor is discharged, and absolute pressure is 2.1-26bar.
In the method provided by the invention, described cyclohexanone-oxime and high-temperature solvent and carrier gas mix vaporization, and the temperature of wherein said solvent and carrier gas is 350～450 ℃, and the temperature of mixed gas is 300～400 ℃ after the vaporization.
In the method provided by the invention, the discharging of described weight-removing column tower reactor is the heavy byproduct that contains hexanolactam, and after forced evaporation unit evaporation, the gas cold that is rich in hexanolactam congeals into and reclaims wherein hexanolactam behind the liquid.Caprolactam content has been reduced to 10% following transmitting system in the resistates after the evaporation of forced evaporation unit.The hexanolactam that the evaporation of forced evaporation unit is reclaimed sends back in the weight-removing column tower reactor, can improve the component of liquid in the weight-removing column tower reactor, is conducive to reduce weight-removing column tower reactor temperature, improves weight-removing column hexanolactam yield.
In the method provided by the invention, described forced evaporation unit is the higher equipment of vaporization efficiency, is preferably luwa evaporator, and it is 130-170 ℃ less than 0.1bar, temperature that the operational condition of luwa evaporator is preferably absolute pressure.The working pressure of described forced evaporation unit is lower than the working pressure of weight-removing column, and for example when weight-removing column operated absolute pressure at 0.1bar, the absolute pressure of the unit of forced evaporation was between 0.06 to 0.1bar.
Specify the embodiment of method provided by the invention below in conjunction with accompanying drawing, accompanying drawing 1 is the method flow synoptic diagram that cyclohexanone-oxime Beckmann rearrangement product separation provided by the invention reclaims hexanolactam, as shown in Figure 1, behind the cyclohexanone-oxime Beckmann rearrangement product desolventizing, through pipeline 11 enter dehydration tower 1 remove in the reaction product with water, dehydration tower 1 operation absolute pressure is 0-0.5bar, and the tower reactor temperature is 100-180 ℃.The dehydration column overhead discharging is water, discharging is the reaction product after dewatering at the bottom of the tower, reaction product after the dehydration enters in the lightness-removing column 2 through pipeline 12, lightness-removing column 2 absolute pressures are that 0-0.5bar, tower reactor temperature are 100-200 ℃, the discharging of lightness-removing column cat head is lighter by product, discharging is the reaction product behind dehydration and the light by product at the bottom of the tower, enters in the weight-removing column 3 through pipeline 13 again, and the operational condition of weight-removing column is: absolute pressure is that 0-0.5bar, tower reactor temperature are 100-200 ℃.The weight-removing column cat head obtains caprolactam product, discharging enters the hexanolactam that forced evaporation unit 4 reclaims wherein at the bottom of containing the tower of the above hexanolactam of 60wt%, gas phase after the evaporation is returned in the weight-removing column 3 after condenser 5 condensations, and the residual liquid phase after the evaporation is the by product discharger.
Comparative Examples
The effect of the thick product separation recovery method of hexanolactam in the Comparative Examples explanation prior art.
Through above treating process, the rate of recovery of hexanolactam is 96%.
Embodiment
Embodiment illustrates the effect of the thick product separation recovery method of hexanolactam provided by the invention.
Flow process as shown in Figure 1, behind the cyclohexanone-oxime Beckmann rearrangement product desolventizing, through pipeline 11 enter remove in the dehydration tower 1 in the reaction product with water, dehydration tower 1 working pressure is 0.1bar, the tower reactor temperature is 135 ℃, the dehydration column overhead discharging is water, discharging is the reaction product after dewatering at the bottom of the tower, and the reaction product after the dehydration enters in the lightness-removing column 2 through pipeline 12, lightness-removing column 2 working pressure 0.013bar, 155 ℃ of tower reactor temperature, the discharging of lightness-removing column cat head is lighter by product, and discharging is the reaction product behind dehydration and the light by product at the bottom of the tower, enters in the weight-removing column 3 through pipeline 13 again, weight-removing column 3 working pressure 0.013bar, 154 ℃ of tower reactor temperature.The weight-removing column cat head obtains caprolactam product, and discharging enters the hexanolactam that forced evaporation unit 4 reclaims wherein at the bottom of the weight-removing column tower, and the gas phase after the evaporation is sent back in the weight-removing column 3 after condenser 5 condensations, and the residual liquid phase after the evaporation is the by product discharger.
Through above treating process, the rate of recovery that obtains hexanolactam is 98%, has improved 2 percentage points than the rate of recovery of traditional process for refining 96%, is equivalent to 400 yuan of product increments per ton, and for producing 100000 tons of devices per year, annual earnings improves 4,000 ten thousand yuan.
Claims (13)
1. the thick product separation of a hexanolactam reclaims the method for hexanolactam, it is characterized in that, the thick product of hexanolactam behind the desolventizing is through dehydration, after taking off light by-product, enter that fractionation removes heavier by product in the weight-removing column, weight-removing column is 0-0.5bar in absolute pressure, the tower reactor temperature is to operate under 100-200 ℃ the condition, cat head obtains caprolactam product, the tower reactor discharging is the heavier by product that contains hexanolactam, the forced evaporation unit is introduced in discharging at the bottom of the tower, at a lower temperature hexanolactam is evaporated, gas phase after the evaporation is returned after condensation in the weight-removing column, and the residual liquid phase after the evaporation is heavier by product discharger.
2. according to the method for claim 1, it is characterized in that described forced evaporation unit is luwa evaporator.
3. according to the method for claim 2, it is characterized in that described luwa evaporator is to operate under 130-170 ℃ the condition less than 0.1bar, temperature in absolute pressure.
4. the method for hexanolactam is produced in a cyclohexanone-oxime vapor phase rearrangement, it is characterized in that, with cyclohexanone-oxime and high-temperature solvent and carrier gas mixing gasifying, introduce in the rearrangement reactor with the gas phase form, filling solid acid catalyst in the rearrangement reactor, cyclohexanone-oxime contacts with solid acid catalyst, it is 200-500 ℃ in temperature, absolute pressure is that reaction generates hexanolactam under the condition of 2.1-26bar, reacted logistics gas-liquid separation after the heat exchange cooling, isolated liquid phase is introduced the thick product of hexanolactam after solvent recovery tower is separated into solvent and desolventizing, the thick product of hexanolactam behind the desolventizing is through dehydration, after taking off light by-product, enter that fractionation removes heavier by product in the weight-removing column, weight-removing column is 0-0.5bar in absolute pressure, the tower reactor temperature is to operate under 100-200 ℃ the condition, cat head obtains caprolactam product, the forced evaporation unit is introduced in the tower reactor discharging, at a lower temperature hexanolactam is evaporated, gas phase after the evaporation is returned after condensation in the weight-removing column, and the residual liquid phase after the evaporation is heavier by product discharger.
5. according to the method for claim 4, it is characterized in that less than 0.1bar, temperature is to operate under 130-170 ℃ the condition in absolute pressure in described forced evaporation unit.
6. according to the method for claim 4 or 5, it is characterized in that, after heat exchange, introduce the flash trapping stage tank by logistics after out the reaction in the rearrangement reactor, be 1-5bar in absolute pressure, temperature is to be separated into gas-liquid two-phase under 60-90 ℃ the condition, and isolated liquid phase is introduced the thick product of hexanolactam that is separated in the solvent recovery tower behind solvent and the desolventizing; The isolated gas phase of flash trapping stage tank is introduced in the second-order separation tank, is separated into gas-liquid two-phase under 20-40 ℃ condition, and wherein liquid phase is returned recycle in the rearrangement reactor after the liquor pump pressurization; Isolated gas phase is mainly carrier gas, returns rearrangement reactor and recycle after the gas compressor pressurization.
7. according to the method for claim 6, it is characterized in that described solid acid catalyst contains HTS, silica zeolite or has the MFI structure molecular screen.
8. according to the method for claim 6, it is characterized in that described solvent is selected from C1-C6 Fatty Alcohol(C12-C14 and C12-C18) or their mixture, the mixture of one or more in particular methanol, ethanol and the propyl alcohol.
9. according to the method for claim 8, the weight ratio that it is characterized in that described solvent and cyclohexanone-oxime is at (10-80): (90-20).
10. according to the method for claim 6, it is characterized in that described inert carrier gas is selected from nitrogen, hydrogen, argon gas, ammonia and boiling point and is not higher than 180 ℃ stable hydrocarbon and one or more the mixture in the halohydrocarbon.
11. according to the method for claim 10, it is characterized in that the mol ratio of described carrier gas and cyclohexanone-oxime is (5-100): 1.
12. according to the method for claim 6, it is characterized in that described forced evaporation unit is luwa evaporator.
13. according to the method for claim 6, it is characterized in that described luwa evaporator is to operate under 130-170 ℃ the condition less than 0.1bar, temperature in absolute pressure.
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| CN111747878A (en) * | 2020-07-14 | 2020-10-09 | 中国石油化工股份有限公司 | Novel caprolactam reduced pressure distillation method |
| CN111848482A (en) * | 2020-08-11 | 2020-10-30 | 湖南百利工程科技股份有限公司 | Separation method of cyclohexanone oxime gas phase reaction rearrangement product |
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| CN114478310A (en) * | 2022-02-24 | 2022-05-13 | 江苏扬农化工集团有限公司 | Gasification method of cyclohexanone oxime and preparation method of caprolactam |
| CN114478344A (en) * | 2022-04-01 | 2022-05-13 | 史秦博苑 | Caprolactam high-efficiency gasification separation process and system |
| CN114507171A (en) * | 2022-02-24 | 2022-05-17 | 江苏扬农化工集团有限公司 | Preparation method of caprolactam |
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| 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 |
| CN106146374B (en) * | 2015-04-02 | 2019-04-26 | 中国石油化工股份有限公司 | A method of recycling cyclohexanone oxime vapour phase rearrangement product fractionation weight raffinate |
| CN106316955A (en) * | 2016-10-28 | 2017-01-11 | 湖北三宁化工股份有限公司 | Refining device for high-purity caprolactam and purifying method |
| CN111747878A (en) * | 2020-07-14 | 2020-10-09 | 中国石油化工股份有限公司 | Novel caprolactam reduced pressure distillation method |
| CN111848515A (en) * | 2020-07-14 | 2020-10-30 | 中国石油化工股份有限公司 | Novel rectification method of caprolactam product |
| CN111848482A (en) * | 2020-08-11 | 2020-10-30 | 湖南百利工程科技股份有限公司 | Separation method of cyclohexanone oxime gas phase reaction rearrangement product |
| CN114478310A (en) * | 2022-02-24 | 2022-05-13 | 江苏扬农化工集团有限公司 | Gasification method of cyclohexanone oxime and preparation method of caprolactam |
| CN114507171A (en) * | 2022-02-24 | 2022-05-17 | 江苏扬农化工集团有限公司 | Preparation method of caprolactam |
| CN114478344A (en) * | 2022-04-01 | 2022-05-13 | 史秦博苑 | Caprolactam high-efficiency gasification separation process and system |
| CN114478344B (en) * | 2022-04-01 | 2024-03-22 | 史秦博苑 | Caprolactam high-efficiency gasification separation process and system |
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