CN114478309A - Preparation method of cyclohexanone oxime steam and preparation method of caprolactam - Google Patents
Preparation method of cyclohexanone oxime steam and preparation method of caprolactam Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/14—Separation; Purification; Stabilisation; Use of additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/30—Accessories for evaporators ; Constructional details thereof
- B01D1/305—Demister (vapour-liquid separation)
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
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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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- C07D223/10—Oxygen atoms attached in position 2
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- C07C2601/14—The ring being saturated
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Abstract
The invention provides a preparation method of cyclohexanone oxime steam. The preparation method comprises the following steps: step S1, introducing the alcohol solution of cyclohexanone oxime and carrier gas into an evaporator for gasification to obtain a gas-liquid mixture containing cyclohexanone oxime; step S2, performing gas-liquid separation on the gas-liquid mixture in a gas-liquid separator to obtain gas-phase cyclohexanone oxime and liquid-phase cyclohexanone oxime, wherein the bottom of the gas-liquid separator is loaded with inorganic alkali; step S3, repeating steps S1 and S2 to gasify the alcoholic solution mixture of liquid-phase cyclohexanone oxime and fresh cyclohexanone oxime and separate gas and liquid. The inorganic base is utilized to stabilize the cyclohexanone-oxime in the gas-liquid separator, particularly to stabilize the liquid-phase cyclohexanone-oxime to be returned to the evaporator, for example, the cyclohexanone-oxime is dissolved in the liquid-phase cyclohexanone-oxime and returns to the evaporator along with the liquid-phase cyclohexanone-oxime, so that the cyclohexanone-oxime in the gasification process is stabilized, the polycondensation coking of the cyclohexanone-oxime in the gasification process is effectively relieved, and the yield of the cyclohexanone-oxime steam is improved.
Description
Technical Field
The invention relates to the technical field of caprolactam preparation, and particularly relates to a preparation method of cyclohexanone oxime steam and a preparation method of caprolactam.
Background
Caprolactam is an important organic chemical raw material, and cyclohexanone oxime is an intermediate product in the production process of caprolactam. At present, cyclohexanone oxime is mainly used as a precursor, and a liquid phase rearrangement method and a gas phase rearrangement method are adopted to prepare caprolactam. Compared with the liquid phase rearrangement method, the gas phase synthesis method is widely applied due to the realization of sulfur-free ammonification of caprolactam.
In the gas phase rearrangement caprolactam synthesis process, cyclohexanone oxime must enter a reactor in a gas phase to participate in the reaction, and the reaction temperature is reached so as to carry out the rearrangement reaction. However, cyclohexanone oxime is a highly heat-sensitive substance, and non-catalytic coking side reactions such as polycondensation and decomposition are easily caused due to uneven heating in the gasification process, so that the problems of raw material loss, catalyst pore channel blockage, catalyst deactivation and the like are caused. Therefore, the cyclohexanone oxime gasification process is a key technology for producing caprolactam by gas phase Beckmann rearrangement.
U.S. Pat. No. 4, 4268440B discloses a cyclohexanone oxime gasification process in which cyclohexanone oxime is gasified by contacting it with inert particles such as silica sand in a fluidized bed in an inert gas atmosphere. This method still cannot avoid decomposition or coking of cyclohexanone oxime in the fluidized bed due to local overheating, resulting in high material consumption in the gasification of cyclohexanone oxime. And the inert particles can not be subjected to continuous coking regeneration, so that coking products block bed channels, the bed pressure drop is increased continuously, and the increase of the bed pressure drop of the fluidized bed needs to be balanced by continuously increasing the inlet pressure of inert gas, so that the operation and control difficulty is high.
Chinese patent CN103055526B discloses a method for evaporating cyclohexanone oxime, wherein cyclohexanone oxime feed liquid is added into a climbing-film evaporator, the steam evaporated from the feed liquid rises at a high speed in the tube to drive the feed liquid to flow upwards in a film shape along the tube wall, the evaporation surface of the climbing-film evaporator is wetted by the cyclohexanone oxime feed liquid, a heating medium is introduced into the other side of the evaporation tube to exchange heat with the feed liquid to gasify part of the feed liquid, the feed liquid and the steam flow upwards to a flash evaporation chamber for gas-liquid separation, cyclohexanone oxime gas is obtained at the top of the flash evaporation chamber, and the unevaporated feed liquid returns to the bottom of the climbing-film evaporator through a circulating tube from the bottom of the flash evaporation chamber to be evaporated continuously. The method still has the situations of incomplete wetting, uneven outside heating and the like, and a small amount of cyclohexanone-oxime still generates coking side reaction to cause the consumption of raw materials.
Disclosure of Invention
The invention mainly aims to provide a preparation method of cyclohexanone oxime steam and a preparation method of caprolactam, which aim to solve the problem of low yield of cyclohexanone oxime steam caused by coking during gasification of cyclohexanone oxime in the prior art.
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for producing cyclohexanone oxime vapor, the method comprising: step S1, introducing the alcohol solution of cyclohexanone oxime and carrier gas into an evaporator for gasification to obtain a gas-liquid mixture containing cyclohexanone oxime; step S2, performing gas-liquid separation on the gas-liquid mixture in a gas-liquid separator to obtain gas-phase cyclohexanone oxime and liquid-phase cyclohexanone oxime, wherein the bottom of the gas-liquid separator is loaded with inorganic alkali; step S3, repeating step S1 and step S2 to gasify the alcoholic solution mixture of liquid-phase cyclohexanone oxime and fresh cyclohexanone oxime and carry out gas-liquid separation.
Further, the inorganic base is selected from any one or more of metal carbonate, metal oxide and metal hydroxide, and preferably, the inorganic base is any one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide and calcium hydroxide.
Further, the mass content of the inorganic base is 1 to 50 wt%, preferably 5 to 30 wt%, with respect to the liquid phase substance in the gas-liquid separator.
Further, the alcohol solvent in the alcohol solution of the cyclohexanone oxime is a saturated alcohol of C1-C6; preferably methanol or ethanol.
Further, the mass content of cyclohexanone oxime in the alcohol solution of cyclohexanone oxime is 5-80 wt%, preferably 20-40 wt%.
Further, the gasification temperature is 120-300 ℃, preferably 160-200 ℃; the pressure of gasification is 0.01 to 0.8MPa, preferably 0.05 to 0.2 MPa.
Further, the carrier gas is any one or more of nitrogen, carbon dioxide and a rare gas, and preferably the rare gas is argon or helium.
Further, the molar ratio of the carrier gas to the cyclohexanone oxime is 5-50: 1, preferably 5-20: 1.
Further, the evaporator is a rising film evaporator, a falling film evaporator or a wiped film evaporator.
According to another aspect of the present invention, there is provided a process for producing caprolactam, comprising gasifying cyclohexanone oxime to obtain gaseous cyclohexanone oxime, subjecting the gaseous cyclohexanone oxime to a gaseous Beckmann rearrangement to obtain caprolactam, and obtaining the gaseous cyclohexanone oxime by any one of the above-described processes.
By applying the technical scheme of the invention, inorganic base is loaded in the gas-liquid separator, and the inorganic base is utilized to stabilize the cyclohexanone oxime in the gas-liquid separator, particularly to stabilize the liquid-phase cyclohexanone oxime to be returned to the evaporator, for example, the liquid-phase cyclohexanone oxime is dissolved in the liquid-phase cyclohexanone oxime and returns to the evaporator along with the liquid-phase cyclohexanone oxime, so that the cyclohexanone oxime in the gasification process is stabilized, the polycondensation coking of the cyclohexanone oxime in the gasification process is effectively relieved, and the steam and the yield of the cyclohexanone oxime are improved. And because the inorganic base is solid, the inorganic base can not enter the subsequent reaction along with the gas-phase cyclohexanone-oxime, so that the subsequent reaction can not be interfered.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background art of the application, the problem of low cyclohexanone oxime vapor yield caused by coking during the gasification of cyclohexanone oxime in the prior art exists. In order to solve the problem, the application provides a preparation method of cyclohexanone oxime steam and a preparation method of caprolactam.
In an exemplary embodiment of the present application, there is provided a method for producing cyclohexanone oxime vapor, the method comprising: step S1, introducing the alcohol solution of cyclohexanone oxime and carrier gas into an evaporator for gasification to obtain a gas-liquid mixture containing cyclohexanone oxime; step S2, performing gas-liquid separation on the gas-liquid mixture in a gas-liquid separator to obtain gas-phase cyclohexanone oxime and liquid-phase cyclohexanone oxime, wherein the bottom of the gas-liquid separator is loaded with inorganic alkali; step S3, repeating step S1 and step S2 to gasify liquid phase cyclohexanone oxime and separate gas and liquid.
According to the method, the inorganic base is loaded in the gas-liquid separator, and the cyclohexanone oxime in the gas-liquid separator is stabilized by the inorganic base, particularly the liquid-phase cyclohexanone oxime to be returned to the evaporator is stabilized, for example, the liquid-phase cyclohexanone oxime is dissolved in the liquid-phase cyclohexanone oxime and returns to the evaporator along with the liquid-phase cyclohexanone oxime, so that the cyclohexanone oxime in the gasification process is stabilized, the polycondensation coking of the cyclohexanone oxime in the gasification process is effectively relieved, and the yield of the cyclohexanone oxime steam is improved. And because the inorganic base is solid, the inorganic base can not enter the subsequent reaction along with the gas-phase cyclohexanone-oxime, so that the subsequent reaction can not be interfered.
The inorganic base used in the present application may be a conventional solid inorganic base, and in order to further control the inorganic base to enter the next reaction along with the gaseous cyclohexanone oxime, the inorganic base is preferably selected from any one or more of metal carbonate, metal oxide and metal hydroxide, and the inorganic base is preferably selected from any one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide and calcium hydroxide. The inorganic bases can keep physical and chemical stabilization under gasification conditions, and further do not bring additional impurities to cyclohexanone oxime.
In order to further improve the stabilization effect of the inorganic base on cyclohexanone oxime, the mass content of the inorganic base on liquid-phase substances in the gas-liquid separator is preferably 1-50 wt%, and preferably 5-30 wt%.
The composition of the alcoholic solution of cyclohexanone oxime can refer to the solution system used in the prior art when cyclohexanone oxime is gasified, for example, the alcoholic solvent in the alcoholic solution of cyclohexanone oxime is a saturated alcohol of C1-C6. Methanol or ethanol is preferable for improving the gasification effect of cyclohexanone oxime.
In order to further control the crosslinking of cyclohexanone oxime in the gasification process, the concentration of cyclohexanone oxime in the alcohol solution of cyclohexanone oxime is further controlled, preferably, the mass content of cyclohexanone oxime in the alcohol solution of cyclohexanone oxime is 5-80 wt%, preferably 20-40 wt%.
The pressure and temperature for gasification can be selected from the pressure and temperature conditions commonly used for cyclohexanone oxime gasification at present, and in some embodiments, the gasification temperature is 120-300 ℃; the gasification pressure is 0.01-0.8 MPa. On the basis of keeping high-efficiency gasification, in order to further avoid the polymerization coking of cyclohexanone oxime in the gasification process, the gasification temperature is preferably 160-200 ℃; the gasification pressure is 0.05-0.2 MPa.
The carrier gas used in the gasification process of the present application can refer to carrier gases commonly used in cyclohexanone oxime gasification in the prior art, for example, the carrier gas is any one or more of nitrogen, carbon dioxide and rare gases, preferably the rare gases are argon and helium. Preferably selected from nitrogen or helium as carrier gas to save cost.
In order to improve the gasification efficiency and ensure the effective concentration of cyclohexanone oxime in the gasified gaseous cyclohexanone oxime, the molar ratio of the carrier gas to cyclohexanone oxime is preferably 5-50: 1, and preferably 5-20: 1.
The above-mentioned gasification reaction of the present application can be applied to a currently conventional vaporizer, for example, the above-mentioned vaporizer is a rising-film vaporizer, a falling-film vaporizer or a wiped-film vaporizer.
In another exemplary embodiment of the present application, there is provided a process for producing caprolactam, comprising vaporizing cyclohexanone oxime to obtain gaseous cyclohexanone oxime, subjecting the gaseous cyclohexanone oxime to gaseous Beckmann rearrangement to obtain caprolactam, and producing the gaseous cyclohexanone oxime by any one of the above-described processes for producing cyclohexanone oxime vapor.
According to the preparation method of the cyclohexanone oxime steam, inorganic alkali is loaded in the gas-liquid separator, and the cyclohexanone oxime in the gas-liquid separator is stabilized by the inorganic alkali, particularly the liquid-phase cyclohexanone oxime to be returned to the evaporator is stabilized, for example, the liquid-phase cyclohexanone oxime is dissolved in the liquid-phase cyclohexanone oxime and returns to the evaporator along with the liquid-phase cyclohexanone oxime, so that the cyclohexanone oxime in the gasification process is stabilized, and the polycondensation coking of the cyclohexanone oxime in the gasification process is effectively relieved. And because the inorganic base is solid, the inorganic base can not enter the Beckmann rearrangement reaction along with the gas-phase cyclohexanone oxime, and the subsequent reaction can not be interfered.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 200g/h and nitrogen at a flow rate of 238L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 160 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone oxime is extracted for the cyclohexanone oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone oxime is continuously pumped into the top of the falling film evaporator for continuous gasification, wherein the bottom of the gas-liquid separatorPartially loaded with Na2CO3，Na2CO3Is 20 wt% of the gas-liquid mixture, and after running continuously for 800h, the clogging of the evaporator is observed and the cyclohexanone oxime content of the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 99.95 percent.
Example 2
Pumping 20 wt% cyclohexanone oxime ethanol solution into a climbing film evaporator from the bottom at a flow rate of 150g/h and nitrogen at a flow rate of 178L/h (nitrogen: cyclohexanone oxime molar ratio of 30), gasifying at a gasification temperature of 200 ℃ and 0.05MPa, wherein the single-pass gasification efficiency is 50%; the gasified gas-liquid mixture enters a gas-liquid separator, the gas-phase cyclohexanone-oxime is extracted for the gas-phase Beckmann rearrangement reaction of the cyclohexanone-oxime, the liquid-phase cyclohexanone-oxime is continuously pumped into the top of a climbing film evaporator for continuous gasification, and NaHCO is loaded at the bottom of the gas-liquid separator3，NaHCO3The loading amount of (b) is 30 wt% of the weight of the liquid phase material in the gas-liquid separator, and after the device is continuously operated for 800 hours, the blockage of the evaporator is observed, and the content of cyclohexanone oxime in the collected cyclohexanone oxime solution is measured. The results show that: the climbing-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 99.90 percent.
Example 3
Pumping a 60 wt% cyclohexanone oxime n-propanol solution into a climbing film evaporator from the bottom at a flow rate of 50g/h and argon at a flow rate of 238L/h (argon: cyclohexanone oxime molar ratio 40), and gasifying at a gasification temperature of 240 ℃ and 0.3MPa with a single-pass gasification efficiency of 40%; the gas-liquid mixture enters a gas-liquid separator, the gas-phase cyclohexanone oxime is extracted for the gas-phase Beckmann rearrangement reaction of the cyclohexanone oxime, the liquid-phase cyclohexanone oxime is continuously pumped into the top of the wiped film evaporator for continuous gasification, and K is loaded at the bottom of the gas-liquid separator2CO3，K2CO3The loading amount of (b) was 40 wt% of the liquid phase substance in the gas-liquid separator, and after the apparatus was continuously operated for 800 hours, the clogging of the evaporator was observed, and the content of cyclohexanone oxime in the collected cyclohexanone oxime solution was measured. The results show that: the wiped film evaporator was not blocked and the cyclohexanone oxime vapor yield was 99.92%.
Example 4
80 wt% cyclohexanone oxime isopropanol solution is pumped into a climbing film evaporator from the bottom at a flow rate of 25g/h and helium at a flow rate of 198L/h (helium: cyclohexanone oxime molar ratio of 50), and is gasified at a gasification temperature of 260 ℃ and 0.2MPa with a single-pass gasification efficiency of 40%; the gas-liquid mixture enters a gas-liquid separator, the gas-phase cyclohexanone oxime is extracted for the gas-phase Beckmann rearrangement reaction of the cyclohexanone oxime, the liquid-phase cyclohexanone oxime is continuously pumped into the top of a climbing film evaporator for continuous gasification, and KHCO is loaded at the bottom of the gas-liquid separator3，KHCO3The loading amount of (b) was 25 wt% of the liquid phase substance in the gas-liquid separator, and after the apparatus was continuously operated for 800 hours, the clogging of the evaporator was observed, and the content of cyclohexanone oxime in the collected cyclohexanone oxime solution was measured. The results show that: the climbing-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 99.95 percent.
Example 5
Pumping 40 wt% cyclohexanone oxime n-butanol solution into a falling film evaporator from the top at a flow rate of 60g/h and carbon dioxide gas at a flow rate of 119L/h (molar ratio of carbon dioxide to cyclohexanone oxime is 25), and gasifying at a gasification temperature of 300 ℃ and 0.4MPa with a single-pass gasification efficiency of 50%; the gas-liquid mixture enters a gas-liquid separator, the gas-phase cyclohexanone oxime is extracted for the gas-phase Beckmann rearrangement reaction of the cyclohexanone oxime, the liquid-phase cyclohexanone oxime is continuously pumped into the top of a falling-film evaporator for continuous gasification, wherein the bottom of the gas-liquid separator is loaded with Ca (OH)2，Ca(OH)2The loading amount of (b) was 10 wt% of the liquid phase substance in the gas-liquid separator, and after the apparatus was continuously operated for 800 hours, the clogging of the evaporator was observed, and the content of cyclohexanone oxime in the collected cyclohexanone oxime solution was measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 99.90 percent.
Example 6
5 wt% cyclohexanone oxime isobutanol solution is pumped into a falling film evaporator from the top at a flow rate of 80g/h and carbon dioxide gas at a flow rate of 8L/h (molar ratio of carbon dioxide to cyclohexanone oxime is 10), and is gasified at a gasification temperature of 220 ℃ and 0.6MPa, wherein the once-through gasification efficiency is 50%; and (2) feeding the gas-liquid mixture into a gas-liquid separator, extracting gas-phase cyclohexanone oxime for a gas-phase Beckmann rearrangement reaction of the cyclohexanone oxime, continuously pumping liquid-phase cyclohexanone oxime into the top of a falling-film evaporator for continuous gasification, wherein NaOH is loaded at the bottom of the gas-liquid separator, the loading capacity of the NaOH is 5 wt% of that of liquid-phase substances in the gas-liquid separator, observing the blockage condition of the evaporator after the device continuously operates for 800 hours, and measuring the content of the cyclohexanone oxime in the collected cyclohexanone oxime solution. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 99.84 percent.
Example 7
Pumping 50 wt% cyclohexanone oxime tert-butanol solution into a climbing film evaporator from the bottom at a flow rate of 100g/h and helium at a flow rate of 50L/h (helium: cyclohexanone oxime molar ratio of 5), and gasifying at a gasification temperature of 120 ℃ and 0.8MPa with a single-pass gasification efficiency of 50%; the gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone oxime is extracted and used for the gas-phase Beckmann rearrangement reaction of the cyclohexanone oxime, liquid-phase cyclohexanone oxime is continuously pumped into the top of a climbing film evaporator to be continuously gasified, KOH is loaded at the bottom of the gas-liquid separator, the loading capacity of the KOH is 50 wt% of that of liquid-phase substances in the gas-liquid separator, after the device is continuously operated for 800 hours, the blockage condition of the evaporator is observed, and the content of the cyclohexanone oxime in the collected cyclohexanone oxime solution is measured. The results show that: the climbing-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 99.93 percent.
Example 8
Pumping 10 wt% cyclohexanone oxime ethanol solution into a falling-film evaporator from the top at a flow rate of 92g/h and nitrogen-argon mixed gas at a flow rate of 64L/h (nitrogen-argon mixed gas: cyclohexanone oxime molar ratio of 35), and gasifying at a gasification temperature of 280 ℃ and under 0.01MPa, wherein the one-way gasification efficiency is 40%; the gas-liquid mixture enters a gas-liquid separator, the gas-phase cyclohexanone oxime is extracted for the gas-phase Beckmann rearrangement reaction of the cyclohexanone oxime, the liquid-phase cyclohexanone oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and K is loaded at the bottom of the gas-liquid separator2CO3，K2CO3The loading amount of (b) was 1 wt% of the liquid phase substance in the gas-liquid separator, and after the apparatus was continuously operated for 800 hours, the clogging of the evaporator was observed, and the content of cyclohexanone oxime in the collected cyclohexanone oxime solution was measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 98.73 percent.
Example 9
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 200g/h and nitrogen at a flow rate of 238L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 160 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; the gasified gas-liquid mixture enters a gas-liquid separator, the gas-phase cyclohexanone-oxime is extracted for the gas-phase Beckmann rearrangement reaction of the cyclohexanone-oxime, the liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 5 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 99.02 percent.
Example 10
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 200g/h and nitrogen at a flow rate of 238L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 160 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 30 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 99.56 percent.
Example 11
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 200g/h and nitrogen at a flow rate of 238L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 160 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; the gas-liquid mixture after partial gasification enters a gas-liquid separator, and gas-phase cyclohexanone oxime is extractedIs used for the gas phase Beckmann rearrangement reaction of the cyclohexanone-oxime, the liquid phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 50 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 98.13 percent.
Example 12
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 200g/h and nitrogen at a flow rate of 238L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 160 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 60 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator was not blocked, and the cyclohexanone oxime vapor yield was 96.90%.
Example 13
A 5 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 182g/h and nitrogen at a flow rate of 36L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 160 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3The loading amount of (A) was 20 wt% of the liquid phase substance in the gas-liquid separator, and after continuous operation for 800 hours, the clogging of the evaporator was observed and the most measuredThe cyclohexanone oxime content of the cyclohexanone oxime solution finally collected. The results show that: the falling film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 98.12 percent.
Example 14
A 20 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 159g/h and nitrogen at a flow rate of 126L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 160 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 20 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 98.78 percent.
Example 15
A 40 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 200g/h and nitrogen at a flow rate of 238L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 160 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 20 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 99.54 percent.
Example 16
80 wt% cyclohexanone oxime in methanol solution at a flow rate of 47g/h and nitrogen at a flow rate of 149L/h (nitrogen: cyclohexanone oxime molar ratio of 20) is removed fromThe top of the mixture is pumped into a falling film evaporator, and the mixture is gasified at the gasification temperature of 160 ℃ and the gasification pressure of 0.1MPa, wherein the one-way gasification efficiency is 50 percent; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 20 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 99.01 percent.
Example 17
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 200g/h and nitrogen at a flow rate of 238L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 120 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 20 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 99.23 percent.
Example 18
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 200g/h and nitrogen at a flow rate of 238L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 200 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; the gas-liquid mixture after partial gasification enters a gas-liquid separator, gas-phase cyclohexanone oxime is extracted for the gas-phase Beckmann rearrangement reaction of cyclohexanone oxime, liquid-phase cyclohexanone oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and the bottom of the gas-liquid separatorLoaded with Na2CO3，Na2CO3Is 20 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 99.75 percent.
Example 19
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 200g/h and nitrogen at a flow rate of 238L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 300 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 20 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 98.78 percent.
Example 20
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling film evaporator from the top at a flow rate of 200g/h and nitrogen at a flow rate of 238L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 100 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 20 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator was not blocked and the cyclohexanone oxime vapor yield was 97.49%.
Example 21
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 200g/h and nitrogen at a flow rate of 238L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 320 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 20 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 98.56 percent.
Example 22
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 200g/h and nitrogen at a flow rate of 238L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 160 ℃ and 0.2MPa, wherein the once-through gasification efficiency is 50%; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 20 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 99.30 percent.
Example 23
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 200g/h and nitrogen at a flow rate of 238L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 160 ℃ and 0.8MPa, wherein the once-through gasification efficiency is 50%; partially gasified gas-liquid mixtureFeeding the obtained cyclohexanone oxime into a gas-liquid separator, collecting the gas-phase cyclohexanone oxime for a gas-phase Beckmann rearrangement reaction of the cyclohexanone oxime, continuously pumping the liquid-phase cyclohexanone oxime into the top of a falling-film evaporator for continuous gasification, wherein the bottom of the gas-liquid separator is loaded with Na2CO3，Na2CO3Is 20 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 98.53 percent.
Example 24
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 200g/h and nitrogen at a flow rate of 238L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 160 ℃ and 0.01MPa, wherein the once-through gasification efficiency is 50%; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 20 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator was not blocked, and the cyclohexanone oxime vapor yield was 97.46%.
Example 25
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 212g/h and nitrogen at a flow rate of 63L/h (nitrogen: cyclohexanone oxime molar ratio of 5), and is gasified at a gasification temperature of 160 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 20 wt% of the liquid phase material in the gas-liquid separator, and continuously operated 800After h, the evaporator was observed for clogging and the cyclohexanone oxime content of the finally collected cyclohexanone oxime solution was measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 98.79 percent.
Example 26
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 36g/h and nitrogen at a flow rate of 107L/h (nitrogen: cyclohexanone oxime molar ratio of 50), and is gasified at a gasification temperature of 160 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 20 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 98.13 percent.
Example 27
Pumping a 30 wt% cyclohexanone oxime methanol solution into a falling-film evaporator from the top at a flow rate of 56g/h and nitrogen at a flow rate of 100L/h (nitrogen: cyclohexanone oxime molar ratio of 30), and gasifying at a gasification temperature of 160 ℃ and 0.1MPa with a single-pass gasification efficiency of 50%; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 20 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, and the yield of the cyclohexanone-oxime vapor is 99.01 percent.
Example 28
30 wt.% cyclohexanone oxime in methanol solution at a flow rate of 72g/h and nitrogen at 25Pumping a flow rate (nitrogen: cyclohexanone oxime molar ratio 60) of 7L/h into the falling-film evaporator from the top, and gasifying at a gasification temperature of 160 ℃ and a gasification temperature of 0.1MPa with a once-through gasification efficiency of 50%; part of the gasified gas-liquid mixture enters a gas-liquid separator, gas-phase cyclohexanone-oxime is extracted for the cyclohexanone-oxime gas-phase Beckmann rearrangement reaction, liquid-phase cyclohexanone-oxime is continuously pumped into the top of the falling-film evaporator for continuous gasification, and Na is loaded at the bottom of the gas-liquid separator2CO3，Na2CO3Is 20 wt% of the liquid phase material in the gas-liquid separator, and after running for 800 hours continuously, the clogging of the evaporator is observed and the cyclohexanone oxime content in the finally collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator was not blocked and the cyclohexanone oxime vapor yield was 97.13%.
Comparative example 1
A 30 wt% cyclohexanone oxime methanol solution is pumped into a falling-film evaporator from the top at a flow rate of 200g/h and nitrogen at a flow rate of 238L/h (nitrogen: cyclohexanone oxime molar ratio of 20), and is gasified at a gasification temperature of 160 ℃ and 0.1MPa, wherein the once-through gasification efficiency is 50%; and part of the gas-liquid mixture enters a gas-liquid separator, the gas-phase cyclohexanone oxime is collected and used for the gas-phase Beckmann rearrangement reaction of the cyclohexanone oxime, the liquid-phase cyclohexanone oxime is continuously pumped into the top of the falling film evaporator for continuous gasification, the blockage condition of the evaporator is observed after the device continuously operates for 800 hours, and the content of the cyclohexanone oxime in the collected cyclohexanone oxime solution is measured. The results show that: the falling-film evaporator is not blocked, but coking is obvious, and the cyclohexanone-oxime vapor yield is 95.23 percent.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
inorganic base is loaded in the gas-liquid separator, and the inorganic base is utilized to stabilize the cyclohexanone oxime in the gas-liquid separator, particularly to stabilize the liquid-phase cyclohexanone oxime to be returned to the evaporator, for example, the liquid-phase cyclohexanone oxime is dissolved in the liquid-phase cyclohexanone oxime and returns to the evaporator along with the liquid-phase cyclohexanone oxime, so that the cyclohexanone oxime in the gasification process is stabilized, the polycondensation coking of the cyclohexanone oxime in the gasification process is effectively relieved, and the yield of the cyclohexanone oxime vapor is improved. And because the inorganic base is solid, the inorganic base can not enter the subsequent reaction along with the gas-phase cyclohexanone-oxime, so that the subsequent reaction can not be interfered.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of cyclohexanone oxime steam is characterized by comprising the following steps:
step S1, introducing the alcohol solution of cyclohexanone oxime and carrier gas into an evaporator for gasification to obtain a gas-liquid mixture containing cyclohexanone oxime;
step S2, carrying out gas-liquid separation on the gas-liquid mixture in a gas-liquid separator to obtain gas-phase cyclohexanone oxime and liquid-phase cyclohexanone oxime, wherein the bottom of the gas-liquid separator is loaded with inorganic alkali;
step S3, repeating the step S1 and the step S2 to gasify the alcoholic solution mixture of the liquid-phase cyclohexanone oxime and the fresh cyclohexanone oxime and carry out gas-liquid separation.
2. The preparation method according to claim 1, wherein the inorganic base is selected from any one or more of metal carbonate, metal oxide and metal hydroxide, preferably the inorganic base is any one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide and calcium hydroxide.
3. The production method according to claim 1 or 2, wherein the inorganic base is contained in an amount of 1 to 50 wt%, preferably 5 to 30 wt%, based on the mass of the liquid-phase substance in the gas-liquid separator.
4. The production method according to any one of claims 1 to 3, characterized in that the alcohol solvent in the alcohol solution of cyclohexanone oxime is a saturated alcohol of C1-C6; preferably methanol or ethanol.
5. The preparation method according to claim 4, wherein the mass content of the cyclohexanone oxime in the alcohol solution of cyclohexanone oxime is 5-80 wt%, preferably 20-40 wt%.
6. The method according to any one of claims 1 to 5, wherein the temperature of the gasification is 120 to 300 ℃, preferably 160 to 200 ℃; the gasification pressure is 0.01-0.8 MPa, preferably 0.05-0.2 MPa.
7. The production method according to claim 1, wherein the carrier gas is any one or more of nitrogen, carbon dioxide and a rare gas, preferably the rare gas is argon and helium.
8. The production method according to any one of claims 1 to 7, wherein the molar ratio of the carrier gas to the cyclohexanone oxime is 5 to 50:1, preferably 5 to 20: 1.
9. The production method according to claim 1, wherein the evaporator is a rising-film evaporator, a falling-film evaporator, or a wiped-film evaporator.
10. A process for producing caprolactam, comprising gasifying cyclohexanone oxime to obtain gaseous cyclohexanone oxime, and subjecting the gaseous cyclohexanone oxime to a gaseous beckmann rearrangement to obtain caprolactam, wherein the gaseous cyclohexanone oxime is obtained by the process according to any one of claims 1 to 9.
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| CN103055526A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Method for evaporating cyclohexanone-oxime |
| CN104557608A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method and device for preparing cyclohexanone oxime gas |
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| US4137263A (en) * | 1976-09-15 | 1979-01-30 | Bayer Aktiengesellschaft | Process for the evaporation of cyclohexanone oxime |
| JPH02193957A (en) * | 1988-11-23 | 1990-07-31 | Basf Ag | Method for improving storage stability of fused cyclohexanone oxime |
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