CN217313418U

CN217313418U - Reaction device for preparing cyclohexanol by hydrating cyclohexene

Info

Publication number: CN217313418U
Application number: CN202220964912.0U
Authority: CN
Inventors: 陈坤; 魏天荣; 孙苏红; 薛耘芸
Original assignee: Hubei Sanning Carbon Phosphorus Based New Material Industry Technology Research Institute Co ltd; Hubei Sanning Chemical Co Ltd
Current assignee: Hubei Sanning Carbon Phosphorus Based New Material Industry Technology Research Institute Co ltd; Hubei Sanning Chemical Co Ltd
Priority date: 2022-04-25
Filing date: 2022-04-25
Publication date: 2022-08-30
Anticipated expiration: 2032-04-25

Abstract

The utility model provides a reaction unit for preparing cyclohexanol by cyclohexene hydration, which comprises a reaction kettle, wherein the upper part of the reaction kettle is connected with a light component rectifying tower through a first heat exchanger, the lower part of the reaction kettle is connected with a heavy component rectifying tower through a second heat exchanger, the lower part and the lower part of the light component rectifying tower are respectively provided with a discharge port, and the upper part and the lower part of the heavy component rectifying tower are also respectively provided with a discharge port; the upper part of the reaction kettle is provided with a raw material feeding hole, and a sprayer is arranged in the reaction kettle and is communicated with the raw material feeding hole. The upper part of the reactor of the device is provided with a light component rectifying device, the lower part of the reactor is connected with a heavy component rectifying tower device, the contact area of water and materials is increased through a sprayer, the yield of cyclohexanol is over 90 percent, and the device can be used for continuous production.

Description

Reaction device for preparing cyclohexanol by hydrating cyclohexene

Technical Field

The utility model belongs to the technical field of chemical industry reaction unit, a reaction unit of cyclohexene hydration preparation cyclohexanol is related to.

Background

Cyclohexanol is an intermediate material for producing adipic acid, caprolactam, medicine, paint, dye and other important chemical products. In the coatings industry, cyclohexanol is commonly used as a solvent for paints, shellacs and varnishes; in the synthetic detergent, cyclohexanol can be used as a stabilizer and a homogenizing agent of the emulsion; cyclohexanol is used in the textile industry as a dye solvent and as a bleach aid.

The current production methods of cyclohexanol mainly comprise a cyclohexane oxidation method, a phenol hydrogenation method, a cyclohexene hydration method and the like. The ethylene oxide process, when mixed with air, can form explosive mixtures and therefore the ethylene oxide process is less safe. The hydrogen consumption of the phenol hydrogenation method is large, and the process is limited to a certain extent. At present, most researches are carried out on a cyclohexene hydration method, wherein the cyclohexene hydration method is divided into a direct hydration method and an indirect hydration method, the direct hydration method is that cyclohexene directly reacts with water to prepare cyclohexanol, but the yield is low, the indirect hydration method is that cyclohexene reacts with carboxylic acid to generate cyclohexyl carboxylate, and the cyclohexyl carboxylate is hydrolyzed to obtain cyclohexanol, and the method can overcome the defects of the cyclohexene direct hydration method, so that the cyclohexanol yield is improved.

Steyer et al in 2002 first proposed a process for producing cyclohexanol by using reactive distillation technology, and the results show that when the Duhelmy number Da is less than 0.109, cyclohexanol can be obtained from the bottom of a reactive distillation column. Further research on Steyer and Sundmacher provides a set of process for producing cyclohexanol by indirect hydration of cyclohexene. The process takes Amberlyst-15wet as a catalyst and formic acid as a reaction entrainer, during the reaction process, cyclohexene reacts with formic acid to generate cyclohexyl formate, and the cyclohexyl formate reacts with water to generate formic acid and cyclohexanol, wherein the formic acid is used as the reaction entrainer for recycling. The two-step reaction is carried out in two reactive distillation columns respectively, but the experimental verification is lacked. The Fuzhou university in 2017 adopts an ion exchange resin A-36 catalyst to perform reactive distillation process flow simulation, but the macroporous resin 15 and the ion exchange resin A-36 have the defects of poor mechanical strength, poor thermal stability, short service life and the like. According to the characteristics of the cyclohexene hydration reaction, a novel reaction device is designed, and the problems in the prior art can be effectively solved.

Disclosure of Invention

The utility model provides a reaction unit of cyclohexene hydration preparation cyclohexanol, the device are used for producing the cyclohexanol have raw materials conversion rate height, product readily releasable, but water and carboxylic acid cyclic utilization's advantage.

The technical scheme of the utility model, a reaction unit of cyclohexene hydration preparation cyclohexanol, including reation kettle, light component rectifying column is connected through first heat exchanger in reation kettle upper portion, and the second heat exchanger is passed through to the reation kettle lower part and is connected heavy component rectifying column, and the lower part of light component rectifying column are equipped with the discharge gate respectively, and the upper portion and the lower part of heavy component rectifying column also are equipped with the discharge gate respectively.

Further, a rectifying column is arranged between the reaction kettle and the first heat exchanger.

Furthermore, a raw material feeding hole is formed in the upper portion of the reaction kettle, a sprayer is arranged in the reaction kettle, and the sprayer is communicated with the raw material feeding hole.

Furthermore, the sprayer is circular, and the diameter is 2~6cm, sets up a plurality of holes on the sprayer.

Furthermore, the upper part of the reaction kettle is in an ellipsoid shape, the raw material feeding hole is positioned on one side of the ellipsoid shape, the sprayer is obliquely arranged 1-5cm away from the wall of the reaction kettle, and the circular surface of the sprayer faces the oblique lower part of the other side of the reaction kettle.

Furthermore, a pipeline between the reaction kettle and the heavy component rectifying tower is obliquely arranged downwards, and the second heat exchanger is also obliquely arranged downwards.

The utility model discloses following beneficial effect has:

1. the cyclohexene hydration prepares esterification reaction and two stages of hydrolysis reaction that the cyclohexanol relates to, the utility model discloses adopt one set of reation kettle with it to produce, need not to change cauldron production, require lowly to equipment, pass through the spray thrower that sets up in reation kettle in the hydrolysis reaction stage moreover, can be with water and raw materials intensive mixing, avoid appearing the problem that the conversion rate is low because of cyclohexene and water are immiscible to lead to, increase the area of contact of water and carboxylic acid cyclohexyl and cyclohexene simultaneously to improve product yield.

2. The utility model discloses set up a plurality of rectifying columns, at esterification reaction and hydrolysis reaction stage, unreacted cyclohexene, water and carboxylic acid can be collected to the light component rectifying column, and the carboxylic acid can be formic acid, acetic acid or propionic acid, does benefit to the recovery and the reuse of raw materials. The heavy component separation tower can further separate the cyclohexyl carboxylate and the cyclohexanol, and the purity of the cyclohexanol is improved.

Drawings

Fig. 1 is a schematic view of the structure of the device of the present invention.

Detailed Description

Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will understand that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.

The utility model provides a reaction unit of cyclohexene hydration preparation cyclohexanol, including reation kettle 1, light component rectifying column 4 is connected through first heat exchanger 3 on reation kettle upper portion, and the reation kettle lower part passes through second heat exchanger 6 and connects heavy ends rectifying column 5, and the lower part of light component rectifying column 4 are equipped with the discharge gate respectively, and the upper portion and the lower part of heavy ends rectifying column 5 also are equipped with the discharge gate respectively.

In a preferable scheme, a rectifying column 2 is also arranged between the reaction kettle and the first heat exchanger 3. The light component and the heavy component can be effectively separated through the rectifying column 2, so that the light component can be recycled.

In the preferred scheme, a raw material feeding hole is formed in the upper portion of the reaction kettle, a sprayer is arranged in the reaction kettle, and the sprayer is communicated with the raw material feeding hole. Through setting up the spray thrower, can increase the area of contact of water and carboxylic acid cyclohexyl and cyclohexene for the reaction is more abundant.

In the preferred scheme, the sprayer is circular, and the diameter is 2~6cm, sets up a plurality of holes on the sprayer.

In the preferred scheme, the upper part of the reaction kettle is in an ellipsoid shape, the raw material feed inlet is positioned on one side of the ellipsoid shape, the sprayer is obliquely arranged 1-5cm away from the wall of the reaction kettle, and the circular surface of the sprayer faces the oblique lower part of the other side of the reaction kettle. The feeding materials can be more uniformly dispersed to the reaction kettle.

In a preferable scheme, a pipeline between the reaction kettle and the heavy component rectifying tower 5 is obliquely arranged downwards, and the second heat exchanger 6 is also obliquely arranged downwards. Facilitating the flow of the heavy fraction.

The specific production comprises the following two reaction links

1) Esterification of cyclohexanol

Adding raw materials cyclohexene and acetic acid into a reaction kettle, introducing nitrogen to remove air, and then closing the nitrogen, wherein the mol ratio of the cyclohexene to the acetic acid is 1: and 3, adding a catalyst ZSM-5, wherein the dosage of the catalyst is 3 percent of the total mass of the reactants, the reaction temperature is 85 ℃, the reaction time is 2 hours, and the pressure is 0.5MPa, so as to obtain the cyclohexyl acetate.

2) Hydrolysis of cyclohexyl carboxylates

To the cyclohexyl acetate obtained in example 1 was added water in a molar ratio of cyclohexyl acetate to water of 1: 2, continuously spraying water in cyclohexyl acetate for reaction by a sprayer in a continuous feeding mode, wherein the reaction temperature is 100 ℃, the reaction time is 3 hours, the pressure is 0.2MPa, and unreacted cyclohexene, water and acetic acid are received by a light component rectifying tower, wherein cyclohexene and water are collected by a discharge port 8 at the upper part of the light component rectifying tower, and acetic acid is collected by a discharge port 9 at the lower part of the light component rectifying tower. The heavy component rectifying tower receives cyclohexyl acetate and cyclohexanol, the cyclohexanol is rectified, the crude yield is more than 90%, the cyclohexanol is collected at a discharge port 10 at the upper part of the heavy component rectifying tower, and the cyclohexyl acetate is collected at a discharge port 11 at the lower part of the heavy component rectifying tower.

Claims

1. The reaction device for preparing cyclohexanol by cyclohexene hydration is characterized in that: including reation kettle (1), light component rectifying column (4) are connected through first heat exchanger (3) in reation kettle upper portion, and heavy ends rectifying column (5) are connected through second heat exchanger (6) in the reation kettle lower part, and the lower part of light component rectifying column (4) are equipped with the discharge gate respectively, and the upper portion and the lower part of heavy ends rectifying column (5) also are equipped with the discharge gate respectively.

2. The apparatus of claim 1, wherein: a rectifying column (2) is also arranged between the reaction kettle and the first heat exchanger (3).

3. The apparatus of claim 1, wherein: the upper part of the reaction kettle is provided with a raw material feeding hole, and a sprayer (7) is arranged in the reaction kettle and is communicated with the raw material feeding hole.

4. The apparatus of claim 3, wherein: the sprayer is circular, and the diameter is 2~6cm, sets up a plurality of holes on the sprayer.

5. The apparatus of claim 3, wherein: the upper part of the reaction kettle is in an ellipsoid shape, the raw material inlet is positioned on one side of the ellipsoid shape, the sprayer is obliquely arranged 1-5cm away from the wall of the reaction kettle, and the circular surface of the sprayer faces the oblique lower part of the other side of the reaction kettle.

6. The apparatus of claim 1, wherein: the pipeline between the reaction kettle and the heavy component rectifying tower (5) is obliquely arranged downwards, and the second heat exchanger (6) is also obliquely arranged downwards.