阅读说明：本技术 一种分离乙醛肟和环己酮的方法 (Method for separating acetaldoxime and cyclohexanone ) 是由 张敏生 赵会娟 张战 党伟荣 陈西波 于 2020-05-07 设计创作，主要内容包括：本发明公开了一种从乙醛肟、乙醛、环己酮和环己酮肟混合物中有效分离出乙醛肟和环己酮的方法,所述方法包括将含有乙醛肟、乙醛、环己酮和环己酮肟的混合物溶液在一定温度和压力下以一定流量加入萃取塔或萃取离心机,采用与水不互溶的有机溶剂和水进行萃取。根据本发明的分离乙醛肟和环己酮的方法采用两种萃取溶剂同时进行萃取,萃取效率高,分离更彻底,可以避免处理过程中的逆反应,同时操作简便,更适合大规模工业化生产。(The invention discloses a method for effectively separating acetaldoxime and cyclohexanone from a mixture of acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime, which comprises the steps of adding a mixture solution containing acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime into an extraction tower or an extraction centrifuge at a certain temperature and pressure and at a certain flow rate, and extracting by adopting an organic solvent and water which are immiscible with water. According to the method for separating the acetaldoxime and the cyclohexanone, two extraction solvents are adopted for extraction at the same time, the extraction efficiency is high, the separation is more thorough, the reverse reaction in the treatment process can be avoided, the operation is simple and convenient, and the method is more suitable for large-scale industrial production.)

1. A process for efficiently separating acetaldoxime and cyclohexanone from a mixture of acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime, the process comprising the steps of:

continuously pumping a mixture solution containing acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime into an extraction tower from a middle feed inlet at a certain temperature and pressure at a certain flow rate, wherein the middle feed inlet is positioned at 1/3-2/3 of the total height from the top of the extraction tower, continuously pumping an organic solvent with density smaller than that of water into the tower from the bottom of the tower, continuously pumping water into the tower from the top of the tower, after stabilization, flowing out a water phase containing water, acetaldehyde and acetaldoxime from the bottom of the tower, and flowing out an oil phase containing cyclohexanone, cyclohexanone oxime and the organic solvent from the top of the tower;

or continuously pumping an organic solvent with the density higher than that of water into the tower from the top of the tower, continuously pumping the water into the tower from the bottom of the tower, after stabilization, flowing out a water phase containing acetaldehyde and acetaldoxime from the top of the tower, and flowing out an oil phase containing cyclohexanone, cyclohexanone oxime and the organic solvent from the bottom of the tower.

2. The process for the separation of aldoxime and cyclohexanone according to claim 1, wherein the process comprises the steps of: continuously pumping a mixture solution containing acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime into a plurality of extraction centrifuges which are connected in series at a certain temperature and pressure at a certain flow rate, discharging or feeding a light phase or a heavy phase from the 2 nd to the 2 nd last in the extraction centrifuges which are connected in series at a feeding position, and after stabilization, if the density of an organic solvent is less than that of water, the heavy phase is a water phase and contains water, acetaldehyde and acetaldoxime, and the light phase is an oil phase and contains cyclohexanone, cyclohexanone oxime and the organic solvent; if the density of the organic solvent is larger than that of water, the light phase is a water phase and contains water, acetaldehyde and acetaldoxime, and the heavy phase is an oil phase and contains cyclohexanone, cyclohexanone oxime and the organic solvent.

3. The method for separating acetaldoxime and cyclohexanone according to claim 1 or 2, wherein the flow ratio of the mixture solution containing acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime to the organic solvent and water is 1:10:10 to 1:0.1:0.1, preferably 1:1:1 to 1:0.5: 0.5.

4. The method for separating acetaldoxime and cyclohexanone according to claim 1 or 2, wherein the extraction is performed at an operating temperature of-20 to 100 ℃, preferably 20 to 50 ℃.

5. The method for separating acetaldoxime and cyclohexanone according to claim 1 or 2, wherein the extraction is performed at an operating pressure of-0.1 to 10MPa, preferably 0 to 0.1 MPa.

6. The method for separating acetaldoxime and cyclohexanone according to claim 1, wherein the extraction column comprises a packed extraction column, a sieve plate extraction column, a turbine extraction column, a rotating disc extraction column, a combination thereof, and the like, and the height of the extraction column can be 1-50 m.

7. The method for separating acetaldoxime and cyclohexanone according to claim 2, wherein the number of the centrifugal extractors is 2 to 50.

8. The method for separating aldoxime and cyclohexanone according to claim 1 or 2, wherein the organic solvent is a water-immiscible solvent, wherein the organic solvent having a density lower than that of water is selected from hydrocarbons and ethers, and the organic solvent having a density higher than that of water is selected from halogenated hydrocarbons and nitro-substituted hydrocarbons.

9. The method for separating aldoxime and cyclohexanone in accordance with claim 8, wherein the hydrocarbon as the organic solvent having density less than water is selected from pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, heptane, cycloheptane, octane, benzene, toluene, xylene, petroleum ether and a mixture thereof, and the ether as the organic solvent having density less than water is selected from dimethyl ether, diethyl ether, n-propyl ether, isopropyl ether, n-butyl ether, isobutyl ether, t-butyl ether, methyl t-butyl ether, ethyl t-butyl ether and a mixture thereof; the halogenated hydrocarbon as the organic solvent with the density higher than that of water is selected from dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethylene, chlorobenzene and mixtures thereof, and the nitro-substituted hydrocarbon as the organic solvent with the density higher than that of water is selected from nitromethane, nitroethane, nitrobenzene and mixtures thereof.

10. The method for separating acetaldoxime and cyclohexanone according to claim 1 or 2, wherein the mixture solution containing acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime is an acetaldoxime reaction solution obtained by subjecting cyclohexanone oxime and acetaldehyde to an oxime exchange reaction, or is obtained by:

(1) adding 300 parts by weight of cyclohexanone-oxime, 280 parts by weight of water, 5 parts by weight of sulfuric acid with the mass percentage concentration of 45% and 233 parts by weight of acetaldehyde into a reactor, stirring at 20-50 ℃ and preserving heat for 1-5 hours to obtain an acetaldoxime reaction solution, wherein the acetaldoxime reaction solution comprises the following components in percentage by weight: 34.30% of water, 18.18% of acetaldoxime, 14.99% of acetaldehyde, 30.73% of cyclohexanone and 1.80% of cyclohexanone oxime;

(2) mixing 300 parts by weight of cyclohexanone oxime, 280 parts by weight of water and 233 parts by weight of acetaldehyde, and continuously passing through strong acid ion exchange resin to obtain an acetaldoxime reaction solution, wherein the acetaldoxime reaction solution comprises the following components in percentage by weight: 34.30% of water, 18.18% of acetaldoxime, 14.99% of acetaldehyde, 30.73% of cyclohexanone and 1.80% of cyclohexanone oxime.

Technical Field

The invention relates to the technical field of chemical separation, and particularly relates to a method for separating acetaldoxime and cyclohexanone from a mixture of acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime.

Background

For example, chinese patent CN104628597A discloses a method for preparing acetaldehyde oxime and 2016, research on new process for synthesis of acetaldehyde oxime, and the above documents do not discuss in detail the separation method of each substance in the reaction system, especially the oxime exchange reaction between acetaldehyde and cyclohexanone oxime, and the azeotropic mixture formed between acetaldehyde oxime and water, cyclohexanone and water, and acetaldehyde oxime and cyclohexanone in the reaction mixture, and the azeotropic points are close to each other, and thus, the acetaldehyde oxime and cyclohexanone cannot be separated and obtained by ordinary rectification technology.

Chinese patent CN110746316A discloses a method for separating and purifying acetaldoxime, which discusses the method for separating and purifying acetaldoxime in an oxime exchange reaction system of acetaldehyde and cyclohexanone oxime, but the method is to add toluene to perform azeotropic distillation first, so that acetaldoxime and toluene form an azeotropic mixture to be distilled out, and thus separate from cyclohexanone, but due to the reversibility of oxime exchange reaction, acetaldehyde is firstly distilled and separated out during the distillation process, chemical equilibrium moves to the left to generate reverse reaction, and inevitably part of acetaldoxime and cyclohexanone undergo reverse reaction to generate acetaldehyde and cyclohexanone oxime, and due to heating during the distillation, the conversion rate of cyclohexanone oxime is reduced, so that acetaldoxime and cyclohexanone cannot be obtained efficiently, which is not an optimal method.

There is therefore still a need to develop improvements in the prior art for separating acetaldoxime and cyclohexanone from a mixture of acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime in a more efficient manner.

Disclosure of Invention

The existing industrial extraction basically adopts single solvent extraction or a mode of carrying out multi-step respective extraction by using a plurality of extracting agents, and for a system containing acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime, effective separation can not be carried out by the single solvent extraction due to the mutual solubility of all substances. The present inventors have made extensive studies and have proposed a continuous double extraction process of a two-solvent to separate acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime, thereby completing the present invention.

In view of the problems of the prior art, according to one aspect of the present invention, it is an object of the present invention to provide a method for efficiently separating acetaldoxime and cyclohexanone from a mixture of acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime, the method comprising the steps of:

continuously pumping a mixture solution containing acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime into an extraction tower from a middle feed inlet at a certain temperature and pressure at a certain flow rate, wherein the middle feed inlet is positioned at 1/3-2/3 of the total height from the top of the extraction tower, continuously pumping an organic solvent with density smaller than that of water into the tower from the bottom of the tower, continuously pumping water into the tower from the top of the tower, after stabilization, flowing out a water phase containing water, acetaldehyde and acetaldoxime from the bottom of the tower, and flowing out an oil phase containing cyclohexanone, cyclohexanone oxime and the organic solvent from the top of the tower;

or continuously pumping an organic solvent with the density higher than that of water into the tower from the top of the tower, continuously pumping the water into the tower from the bottom of the tower, after stabilization, flowing out a water phase containing acetaldehyde and acetaldoxime from the top of the tower, and flowing out an oil phase containing cyclohexanone, cyclohexanone oxime and the organic solvent from the bottom of the tower.

Or continuously pumping the mixture solution containing acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime into a plurality of extraction centrifuges which are connected in series at a certain temperature and pressure at a certain flow rate, discharging or feeding a light phase or a heavy phase from the 2 nd to the 2 nd last in the extraction centrifuges which are connected in series at a feeding position, and after stabilization, if the density of the organic solvent is less than that of water, the heavy phase is a water phase and contains water, acetaldehyde and acetaldoxime, and the light phase is an oil phase and contains cyclohexanone, cyclohexanone oxime and the organic solvent; if the density of the organic solvent is larger than that of water, the light phase is a water phase and contains water, acetaldehyde and acetaldoxime, and the heavy phase is an oil phase and contains cyclohexanone, cyclohexanone oxime and the organic solvent.

The flow ratio of the mixture solution containing the acetaldoxime, the acetaldehyde, the cyclohexanone and the cyclohexanone oxime to the organic solvent and the water is 1:10:10 to 1:0.1:0.1, preferably 1:1:1 to 1:0.5: 0.5.

The extraction temperature is-20 to 100 ℃, preferably 20 to 50 ℃.

The operation pressure of the extraction is-0.1-10 MPa, preferably 0-0.1 MPa.

Preferably, the extraction tower comprises a packing extraction tower, a sieve plate extraction tower, a turbine extraction tower, a rotary disc extraction tower, a combination thereof and the like, and the height of the extraction tower can be 1-50 meters.

Preferably, the number of the centrifugal extractors is 2-50.

Preferably, the organic solvent is a water-immiscible solvent, wherein the organic solvent with density less than water is selected from hydrocarbons and ethers, and the organic solvent with density greater than water is selected from halogenated hydrocarbons and nitro-substituted hydrocarbons.

Preferably, the hydrocarbon as the organic solvent having a density less than water is selected from pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, heptane, cycloheptane, octane, benzene, toluene, xylene, petroleum ether, etc., and mixtures thereof, and the ether as the organic solvent having a density less than water is selected from dimethyl ether, diethyl ether, n-propyl ether, isopropyl ether, n-butyl ether, isobutyl ether, t-butyl ether, methyl t-butyl ether, ethyl t-butyl ether, etc., and mixtures thereof; the halogenated hydrocarbon as the organic solvent with the density higher than that of water is selected from dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethylene, chlorobenzene and the like and mixtures thereof, and the nitro-substituted hydrocarbon as the organic solvent with the density higher than that of water is selected from nitromethane, nitroethane, nitrobenzene and the like and mixtures thereof.

Preferably, the mixture solution containing acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime is an acetaldoxime reaction solution prepared by performing an oxime exchange reaction between cyclohexanone oxime and acetaldehyde, and the reaction solution may or may not contain water, or may be prepared according to the following method: (1) adding 300 parts by weight of cyclohexanone-oxime, 280 parts by weight of water, 5 parts by weight of sulfuric acid with the mass percentage concentration of 45% and 233 parts by weight of acetaldehyde into a reactor, stirring at 20-50 ℃ and preserving heat for 1-5 hours to obtain an acetaldoxime reaction solution, wherein the acetaldoxime reaction solution comprises the following components in percentage by weight: 34.30% of water, 18.18% of acetaldoxime, 14.99% of acetaldehyde, 30.73% of cyclohexanone and 1.80% of cyclohexanone oxime. (2) Mixing 300 parts by weight of cyclohexanone oxime, 280 parts by weight of water and 233 parts by weight of acetaldehyde, and continuously passing through strong acid ion exchange resin to obtain an acetaldoxime reaction solution, wherein the acetaldoxime reaction solution comprises the following components in percentage by weight: 34.30% of water, 18.18% of acetaldoxime, 14.99% of acetaldehyde, 30.73% of cyclohexanone and 1.80% of cyclohexanone oxime.

Advantageous effects

According to the method for separating the acetaldoxime and the cyclohexanone, two extraction solvents are adopted for extraction at the same time, the extraction efficiency is high, the separation is more thorough, the reverse reaction in the treatment process can be avoided, the operation is simple and convenient, and the method is more suitable for large-scale industrial production.

Detailed Description

Hereinafter, the present invention will be described in detail. Before the description is made, it should be understood that the terms used in the present specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.

According to the method for effectively separating the acetaldoxime and the cyclohexanone from the acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime mixture, the mixture solution containing the acetaldoxime, the acetaldehyde, the cyclohexanone and the cyclohexanone oxime is continuously pumped into the middle part of an extraction tower (or a series extraction centrifuge combination), an organic solvent which has a density smaller than that of water and is immiscible with water is continuously pumped from the bottom of the extraction tower, another solvent water is continuously pumped from the top of the extraction tower, after stabilization, an oil phase flowing out from the top of the extraction tower is basically free of acetaldoxime and acetaldehyde, and a water phase at the bottom of the extraction tower is basically free of cyclohexanone and cyclohexanone oxime; if the density of the organic solvent is greater than that of water, the organic solvent which is greater than that of water and is immiscible with water is continuously pumped from the top of the tower, the other solvent water is continuously pumped from the bottom of the tower, after stabilization, the oil phase flowing out from the bottom of the tower is basically free of acetaldoxime and acetaldehyde, and the water phase at the top of the tower is basically free of cyclohexanone and cyclohexanone oxime. The acetaldehyde oxime and acetaldehyde almost completely enter a water phase, and the cyclohexanone and cyclohexanone oxime almost completely enter an oil phase, so that the acetaldehyde oxime and the cyclohexanone are firstly completely separated, and the water phase and the oil phase are respectively rectified by a common rectifier to obtain pure acetaldehyde oxime aqueous solution and pure cyclohexanone, so that the occurrence of reverse reaction is avoided, and unreacted acetaldehyde and cyclohexanone oxime are recycled, so that the acetaldehyde and cyclohexanone oxime can be conveniently used for producing the acetaldehyde oxime and the byproduct cyclohexanone oxime. The method has no three-waste discharge and low cost. The following examples are given.

The flow ratio of the mixture solution containing acetaldoxime, acetaldehyde, cyclohexanone and cyclohexanone oxime to the organic solvent and water according to the extraction separation method of the present invention is 1:10:10 to 1:0.1:0.1, preferably 1:1:1 to 1:0.5: 0.5. When the ratio is within the above range, the extraction separation effect is optimal. If the amount of water or organic solvent used as the extractant is too large, the extraction effect is improved, but the method is not economical, and the later-stage wastewater treatment amount is large and is not environment-friendly; if the amount of water or organic solvent used as an extractant is too small, the extraction effect is not satisfactory.

The operation temperature of extraction is 0 ~ 100 ℃, preferably, 20 ~ 50 ℃, and the optimum is the environment natural temperature, when the extraction temperature is less than 20 ℃ or is higher than 50 ℃, needs additionally to cool off or heat the material, has increased the energy consumption, and is little to the extraction efficiency influence, and probably takes place the reverse reaction during the heating.

The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.

Example 1:

preparing a reaction solution: adding 300 g of cyclohexanone oxime, 280 g of water, 5 g of 45% sulfuric acid and 233 g of acetaldehyde into a reaction bottle, stirring at 30 ℃ and preserving heat for 1-5 hours to obtain an acetaldoxime reaction solution, wherein the acetaldoxime reaction solution comprises the following components in percentage by mass: 34.30% of water, 18.18% of acetaldoxime, 14.99% of acetaldehyde, 30.73% of cyclohexanone and 1.80% of cyclohexanone oxime.

The reaction liquid is continuously pumped into an extraction tower which is filled with 3 multiplied by 3 dicke pine packing and has the diameter of 30mm and the height of 2600mm from the middle part at the temperature of 30 ℃ and the normal pressure, the flow rate is 2ml/min, the height of a lower packing layer at a feeding position is 1500mm, the height of an upper packing layer is 1100mm, the extraction tower is filled with water, toluene is continuously pumped into the tower from the bottom of the tower, the flow rate is 2ml/min, water is continuously pumped into the tower from the top of the tower, the flow rate is 1.5ml/min, water is a continuous phase, toluene is a disperse phase, and after 2 hours, the water phase flowing out from the bottom of the tower consists of the following water phases in percentage by mass: 79.13% of water, 10.64% of acetaldehyde, 10.23% of acetaldoxime, 0.00% of cyclohexanone and 0.00% of cyclohexanone oxime. The oil phase flowing out of the tower top comprises the following components in percentage by mass: 4.09% of acetaldehyde, 0.00% of acetaldoxime, 27.43% of cyclohexanone, 1.02% of cyclohexanone oxime and 67.46% of toluene.

Rectifying the water phase by a rectifying tower, controlling the rectifying temperature to be 100 ℃, the tower top temperature to be 92-96 ℃, and the reflux ratio to be 1: 3, obtaining the acetaldoxime product.

Rectifying the oil phase by a rectifying tower, controlling the rectifying temperature within 150 ℃, and carrying out reduced pressure rectification with the reflux ratio of 1: 1- - -1: and 9, collecting fractions according to different temperatures to respectively obtain toluene and cyclohexanone.

The water phase is rectified to form: the content of acetaldoxime is 49.55%, the water content is 50.45%, and the purity of acetaldoxime is 99.96%. The oil phase is rectified to obtain 99.99 percent of toluene and 99.98 percent of cyclohexanone.

Example 2:

preparing a reaction solution: adding 300 g of cyclohexanone-oxime, 280 g of water and 233 g of acetaldehyde into a reaction bottle, uniformly mixing, continuously stirring, pumping into a columnar reactor filled with macroporous strong-acid ion exchange resin, and enabling the volume space velocity to be 0.5h^-1And the reaction temperature is 50 ℃, so that an acetaldoxime reaction solution is obtained, and comprises the following components in percentage by mass: 34.30 percent of water, 18.18 percent of acetaldoxime, 14.99 percent of acetaldehyde, 30.73 percent of cyclohexanone,1.80 percent of cyclohexanone oxime.

The reaction solution is continuously pumped into an extraction tower which is filled with 3 multiplied by 3 dicke pine packing and has the diameter of 30mm and the height of 2600mm from the middle part at the temperature of 50 ℃ and normal pressure, the flow rate is 2ml/min, the height of a lower packing layer at a feeding position is 1500mm, the height of an upper packing layer is 1100mm, the extraction tower is filled with water, toluene is continuously pumped into the tower from the bottom of the tower, the flow rate is 2ml/min, water is continuously pumped into the tower from the top of the tower, the flow rate is 1.5ml/min, toluene is a continuous phase, water is a disperse phase, and after 2 hours, the water phase flowing out from the bottom of the tower consists of the following water phases in percentage by mass: 79.11 percent of water, 10.34 percent of acetaldehyde, 10.55 percent of acetaldoxime, 0.00 percent of cyclohexanone and 0.00 percent of cyclohexanone oxime. The composition of the oil phase flowing out of the tower top is as follows: 3.88% of acetaldehyde, 0.00% of acetaldoxime, 26.55% of cyclohexanone, 1.10% of cyclohexanone oxime and 68.47% of toluene.

Example 3:

preparing a reaction solution: same as in example 2.

The reaction liquid is continuously pumped into an extraction tower which is provided with 3 multiplied by 3 dicke pine packing and has the diameter of 30mm and the height of 2600mm at the temperature of 50 ℃ and the pressure of 0.1MPa from the middle part, the flow rate is 2ml/min, the height of a lower packing layer at a feeding position is 1500mm, the height of an upper packing layer is 1100mm, the extraction tower is filled with water, cyclohexane is continuously pumped into the tower from the bottom of the tower, the flow rate is 2ml/min, water is continuously pumped into the tower from the top of the tower, the flow rate is 1.5ml/min, water is a continuous phase, cyclohexane is a disperse phase, and after 2 hours, the water phase flowing out from the bottom of the tower consists of the following water phases in percentage by mass: 72.38% of water, 12.11% of acetaldehyde, 15.51% of acetaldoxime, 0.00% of cyclohexanone and 0.00% of cyclohexanone oxime. The composition of the oil phase flowing out of the tower top is as follows: 3.99% of acetaldehyde, 0.00% of acetaldoxime, 26.11% of cyclohexanone, 1.11% of cyclohexanone oxime and 68.79% of cyclohexane.

Example 4:

preparing a reaction solution: same as in example 2.

The reaction liquid is continuously pumped into an extraction tower which is provided with 3 multiplied by 3 dicke pine packing and has the diameter of 30mm and the height of 2600mm at the temperature of 20 ℃ and the pressure of 0.1MPa from the middle part, the flow rate is 2ml/min, the height of a lower packing layer at a feeding position is 1500mm, the height of an upper packing layer is 1100mm, the extraction tower is filled with cyclohexane, the cyclohexane is continuously pumped into the tower from the bottom of the tower, the flow rate is 2ml/min, water is continuously pumped into the tower from the top of the tower, the flow rate is 1.5ml/min, the cyclohexane is a continuous phase, the water is a disperse phase, and after 2 hours, the water phase flowing out from the bottom of the tower consists of the following water phases in percentage by mass: 73.46% of water, 12.55% of acetaldehyde, 13.99% of acetaldoxime, 0.00% of cyclohexanone and 0.00% of cyclohexanone oxime. The composition of the oil phase flowing out of the tower top is as follows: 4.46% of acetaldehyde, 0.00% of acetaldoxime, 26.11% of cyclohexanone, 1.09% of cyclohexanone oxime and 68.34% of cyclohexane.

Example 5:

preparing a reaction solution: same as in example 2.

The reaction solution is continuously pumped into an extraction tower which is filled with 3 multiplied by 3 dicke pine packing and has the diameter of 30mm and the height of 2600mm from the middle part at the temperature of 35 ℃ and normal pressure, the flow rate is 2ml/min, the height of a lower packing layer at a feeding position is 1500mm, the height of an upper packing layer is 1100mm, the extraction tower is filled with water, methyl tert-butyl ether is continuously pumped into the tower from the bottom of the tower, the flow rate is 2ml/min, water is continuously pumped into the tower from the top of the tower, the flow rate is 1.5ml/min, the water is a continuous phase, the methyl tert-butyl ether is a disperse phase, and after 2 hours, the water phase flowing out from the bottom of the tower consists of the following water phases: 75.25% of water, 11.12% of acetaldehyde, 13.63% of acetaldoxime, 0.00% of cyclohexanone and 0.00% of cyclohexanone oxime. The composition of the oil phase flowing out of the tower top is as follows: acetaldehyde 4.99%, acetaldoxime 0.00%, cyclohexanone 25.11%, cyclohexanone oxime 1.21%, methyl tert-butyl ether 68.69%.

Example 6:

preparing a reaction solution: same as in example 2.

The reaction solution is continuously pumped into an extraction tower which is filled with 3 multiplied by 3 dicke pine packing and has the diameter of 30mm and the height of 2600mm from the middle part at the temperature of 30 ℃ and the normal pressure, the flow rate is 2ml/min, the height of a packing layer at the lower part of a feeding position is 1500mm, the height of a packing layer at the upper part is 1100mm, the extraction tower is filled with methyl tert-butyl ether, the methyl tert-butyl ether is continuously pumped into the tower from the bottom of the tower, the flow rate is 2ml/min, water is continuously pumped into the tower from the top of the tower, the flow rate is 1.5ml/min, the water is a disperse phase, and the methyl tert-butyl ether is a continuous phase. After 2 hours, the aqueous composition of the bottom stream: 78.35% of water, 10.12% of acetaldehyde, 11.53% of acetaldoxime, 0.00% of cyclohexanone and 0.00% of cyclohexanone oxime. The composition of the oil phase flowing out of the tower top is as follows: 6.59% of acetaldehyde, 0.00% of acetaldoxime, 26.11% of cyclohexanone, 1.22% of cyclohexanone oxime and 66.08% of methyl tert-butyl ether.

Example 7:

preparing a reaction solution: same as in example 2.

The reaction liquid is continuously pumped into an extraction tower which is filled with 3 multiplied by 3 dicke pine packing and has the diameter of 30mm and the height of 2600mm from the middle part at the temperature of 30 ℃ and the normal pressure, the flow rate is 2ml/min, the height of a lower packing layer at a feeding position is 1500mm, the height of an upper packing layer is 1100mm, the extraction tower is filled with water, the water is continuously pumped into the tower from the bottom of the tower, the flow rate is 1.5ml/min, dichloromethane is continuously pumped into the tower from the top of the tower, the flow rate is 2ml/min, the water is a continuous phase, the dichloromethane is a disperse phase, and after 2 hours, the water phase flowing out from the top of the tower consists of the following water phases: 79.15% of water, 10.32% of acetaldehyde, 10.53% of acetaldoxime, 0.00% of cyclohexanone and 0.00% of cyclohexanone oxime. The oil phase flowing out of the tower bottom consists of: 5.59% of acetaldehyde, 0.00% of acetaldoxime, 27.11% of cyclohexanone, 1.13% of cyclohexanone oxime and 66.17% of dichloromethane.

Example 8:

preparing a reaction solution: same as in example 2.

The reaction solution is continuously pumped into an extraction tower which is filled with 3 multiplied by 3 dicke pine packing and has the diameter of 30mm and the height of 2600mm at the temperature of 40 ℃ and the pressure of 0.1MPa from the middle part, the flow rate is 2ml/min, the height of a packing layer at the lower part of a feeding position is 1500mm, the height of a packing layer at the upper part is 1100mm, the extraction tower is filled with dichloromethane, water is continuously pumped into the tower from the bottom of the tower, the flow rate is 1.5ml/min, dichloromethane is continuously pumped into the tower from the top of the tower, the flow rate is 2ml/min, water is a disperse phase, and dichloromethane is a continuous phase. After 2 hours, the aqueous phase composition flowing out of the top of the column: 77.15% of water, 11.33% of acetaldehyde, 11.52% of acetaldoxime, 0.00% of cyclohexanone and 0.00% of cyclohexanone oxime. The oil phase flowing out of the tower bottom consists of: 6.59% of acetaldehyde, 0.00% of acetaldoxime, 28.21% of cyclohexanone, 1.15% of cyclohexanone oxime and 64.05% of dichloromethane.

Example 9:

preparing a reaction solution: same as in example 1.

Continuously pumping the reaction solution into 8 centrifugal extractors connected in series from a 5 th extraction centrifuge at 30 ℃ and 0.05MPa, wherein the flow rate is 2ml/min, toluene is continuously pumped into the centrifuges from a light phase sample inlet of the first extraction centrifuge, the flow rate is 2ml/min, water is continuously pumped into the centrifuges from a heavy phase sample inlet of the last extraction centrifuge, the flow rate is 1.5ml/min, and the aqueous phase composition flowing out of a heavy phase outlet of the first extraction centrifuge is formed after 2 hours: 76.00% of water, 12.55% of acetaldehyde, 11.45% of acetaldoxime, 0.00% of cyclohexanone and 0.00% of cyclohexanone oxime. The oil phase flowing out of the light phase outlet of the last extraction centrifuge comprises the following components: 5.09% of acetaldehyde, 0.00% of acetaldoxime, 25.43% of cyclohexanone, 1.02% of cyclohexanone oxime and 68.46% of toluene.