Device for continuously and mildly producing cyclohexene oxide without catalyst

Abstract

The utility model provides a device for continuously and mildly producing cyclohexene oxide without a catalyst, which comprises a reaction tank, a liquid enhanced reactor is arranged at the inner top of the reaction tank, and a mixing pipeline is externally connected with the liquid enhanced reactor. The mixing pipeline is formed by converging a first circulating pipeline, a second circulating pipeline and a third circulating pipeline through a liquid mixer 1, and the first circulating pipeline is used for reaction; the second circulating pipeline is used for separation and recovery; the third circulating pipeline is used for refining, and the first circulating pipeline, the second circulating pipeline and the third circulating pipeline are connected in parallel. According to the device, side reactions can be reduced to a great extent through the design of the pipeline and the application of the enhanced reactor, the reaction efficiency and the conversion rate of raw materials are improved, the reaction cost can be reduced, and the concept of green chemistry is better met.

Description

Technical Field

[0001] The utility model belongs to the technical field of chemical industry, in particular to a device for continuously and gently producing cyclohexene oxide without catalyst. Background Art

[0002] Epoxycyclohexane is the primary raw material for the synthesis of the pesticide propargite, and market demand for it has been growing in recent years. However, traditional methods for producing epoxycyclohexane are plagued by long reaction times, high costs, and difficulty meeting environmental standards. A new method for producing epoxycyclohexane using cyclohexene as a raw material has emerged in recent years. These methods, depending on the oxygen source, can be categorized as organic peroxide epoxidation, hypochlorous acid, or electrochemical. However, significant pollution, equipment corrosion, numerous side reactions, and high costs remain to be overcome. Therefore, research and development of economical and environmentally friendly technologies for producing high-purity epoxycyclohexane are of vital importance.

[0003] In view of this, the present utility model is proposed. Utility Model Content

[0004] The first purpose of the utility model is to provide a device for continuously and gently producing cyclohexene oxide without a catalyst. The device can greatly reduce the occurrence of side reactions through the design of pipelines and the application of enhanced reactors, improve reaction efficiency and raw material conversion rate, and at the same time reduce reaction costs, which is more in line with the concept of green chemistry.

[0005] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are adopted:

[0006] The utility model provides a device for continuously and gently producing cyclohexene oxide without a catalyst, comprising:

[0007] A reaction tank is provided with a liquid enhancement reactor on the inner top of the reaction tank. The liquid enhancement reactor is connected to an external mixing pipeline. The mixing pipeline is formed by the first circulation pipeline, the second circulation pipeline and the third circulation pipeline being combined through a liquid mixer 1. The first circulation pipeline is used for reaction; the second circulation pipeline is used for separation and recovery; the third circulation pipeline is used for refining. The first circulation pipeline, the second circulation pipeline and the third circulation pipeline are connected in parallel.

[0008] Preferably, as a further specific embodiment, a gas intensification reactor is provided at the inner bottom of the reaction tank, and the gas intensification reactor is directly connected to the gas delivery pump provided at the bottom of the reaction tank; a pipeline is provided on the side wall of the reaction tank to connect with the flash tank, and a pipeline is provided at the bottom of the flash tank to form a first circulation pipeline through the liquid mixer 1 and the mixing pipeline.

[0009] Preferably, as a further specific embodiment, the inlets of the first circulation pipeline and the second circulation pipeline are connected in parallel through a flash tank, the top of the flash tank is provided with a pipeline connected to the middle of the side wall of the product separation tower, the top of the product separation tower is provided with a pipeline connected to the middle of the side wall of the recovery tower, and the top outlet of the recovery tower is provided with a pipeline forming a collecting pipe through a liquid mixer 2, and the collecting pipe is merged into the mixing pipeline through the liquid mixer 1 to form the second circulation pipeline; the product separation tower and the recovery tower are connected in series.

[0010] Preferably, as a further specific embodiment, the inlets of the second circulation pipeline and the third circulation pipeline are connected in parallel through the separation tower, the bottom of the separation tower is provided with a pipeline connected to the middle of the side wall of the product refining tower, and the top outlet of the product refining tower is provided with a pipeline forming a collecting pipe through the liquid mixer 2, and the collecting pipe merges into the mixing pipeline through the liquid mixer 1 to form the third circulation pipeline.

[0011] Preferably, as a further specific embodiment, the product separation tower, recovery tower and product refining tower are all equipped with a condenser, a reboiler and a reflux tank.

[0012] Preferably, as a further specific embodiment, the reaction device further comprises a raw material premixer, and the raw material premixer enters the mixing pipeline through the liquid mixer 1 and is connected to the reaction tank.

[0013] Preferably, as a further specific embodiment, the raw material premixer is directly connected to the raw material storage tank, and a stirring paddle is provided inside the raw material premixer, and the stirring paddle is located at 1 / 3-1 / 2 from the bottom of the raw material premixer.

[0014] Preferably, as a further specific embodiment, the product separation tower, recovery tower and product refining tower are all provided with tower plates, the total number of tower plates of the product separation tower is 15-30; the total number of tower plates of the recovery tower is 15-35; the total number of tower plates of the product refining tower is 20-40.

[0015] Compared with the prior art, the beneficial effects of the present invention are:

[0016] (1) Through the gas-enhanced reactor and the liquid-enhanced reactor, the gas-liquid two-phase materials can be reversely offset, which increases the residence and retention time of the micro-droplets, improves the mass transfer effect between the reaction materials, and improves the reaction efficiency.

[0017] (2) During the reaction stage, the reaction is carried out at room temperature and pressure without using a catalyst. The operating conditions are mild, which greatly improves the safety and environmental benefits of the reaction process. During the separation and refining of the cyclohexene oxide product, the reaction is carried out at room pressure without using a high-pressure tower, thus avoiding the occurrence of other side reactions. The material recovery system can recover almost all solvents, electrolytes and unreacted materials, and at the same time obtain high-purity by-product cyclohexanone, which can improve economic benefits.

[0018] (3) Through the design of the pipeline, the reaction raw materials can be efficiently utilized, and the high-purity by-products produced during the reaction process can be promptly recovered and utilized to avoid the by-products from entering the reaction again.

[0019] BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 : Example 1 is a schematic diagram of the structure of a device for continuously and gently producing cyclohexene oxide without a catalyst;

[0020] Figure 2 : Schematic diagram of the first circulation pipeline in Example 1;

[0021] Figure 3 : Schematic diagram of the second circulation pipeline in Example 1;

[0022] Figure 4 : Schematic diagram of the third circulation pipeline in Example 1.

[0023] in:

[0024] 1-reaction tank, 2-liquid enhanced reactor, 3-gas enhanced reactor, 4-flash tank, 5-product separation tower,

[0025] 6- Recovery tower, 7- Product refining tower, 8- Raw material premixer, 9- Liquid mixer 3, 10- Liquid mixer 1,

[0026] 11-Liquid mixer 2, 12-Reboiler 1, 13-Reboiler 2, 14-Reboiler 3, 15-Reflux tank 1,

[0027] 16- Reflux tank 2, 17- Reflux tank 3, 18- Condenser 1, 19- Condenser 2, 20- Condenser 3,

[0028] 21-delivery pump 1, 22-delivery pump 2, 23-delivery pump 3, 24-delivery pump 4, 25-delivery pump 5,

[0029] 26-delivery pump 6, 27-delivery pump 7, 28-delivery pump 8, 29-delivery pump 9, 30-delivery pump 10,

[0030] 31-delivery pump 11, 32-delivery pump 12, 33-stirring paddle, 34-first circulation pipeline, 35-second circulation pipeline,

[0031] 36- The third circulation pipeline. DETAILED DESCRIPTION

[0032] The technical solution of the present invention will be clearly and completely described below in conjunction with specific embodiments, but those skilled in the art will understand that the embodiments described below are part of the embodiments of the present invention, rather than all of the embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention. If specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0033] In the description of this utility model, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicating positions or relationships, are based on the positions or relationships shown in the accompanying drawings and are intended solely to facilitate the description of this utility model and simplify the description. They do not indicate or imply that the devices or components referred to must have a specific orientation, be constructed, or operate in a specific orientation. Therefore, they should not be construed as limitations on this utility model. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0034] In the description of this utility model, it should be noted that, unless otherwise expressly specified or limited, the terms "mounted," "connected," and "connected" should be understood in a broad sense. For example, they can refer to fixed connections, detachable connections, or integral connections; mechanical connections, electrical connections; direct connections, indirect connections through an intermediate medium, and internal communication between two components. Those skilled in the art will understand the specific meanings of the above terms in this utility model based on the specific circumstances.

[0035] In order to more clearly illustrate the technical solution of the present invention, it is described below in the form of specific embodiments.

[0036] Example 1

[0037] See Figure 1As shown, the apparatus for the catalyst-free, continuous, gentle production of cyclohexane oxide according to an embodiment of the present invention includes an 8-material premixer. The 8-material premixer can be directly connected to a material storage tank or can be mixed with the material storage tank via a 9-liquid mixer 3. In this embodiment, water, cyclohexene, and acetonitrile (as shown in Table 1) enter the 8-material premixer through the 9-liquid mixer 3 for stirring. Tetrabutylammonium bromide enters the 8-material premixer directly to stir with the premixed materials. Furthermore, the stirring paddle 33 in the 8-material premixer is positioned one-third of the way from the bottom of the 8-material premixer. Because the reaction materials will eventually converge at the bottom of the 8-material premixer due to gravity, the stirring paddle 33 is positioned slightly downward to ensure that all materials are fully premixed before entering the 1-reaction tank, facilitating subsequent reactions.

[0038] The premixed raw materials are transported through the 21-delivery pump 1, subjected to secondary mixing through the 10-liquid mixer 1, and then enter the 1-reaction tank through the mixing pipeline. At this time, the reaction temperature in the 1-reaction tank is 15°C-30°C, and the reaction pressure varies between 0.8atm-2atm. A 2-liquid enhanced reactor is provided on the top of the 1-reaction tank, and a nozzle is provided at the outlet of the 2-liquid enhanced reactor. The nozzle can perform secondary mixing and atomization spraying of the premixed micro-droplets, providing power for the reaction raw materials and accelerating the reaction process. At the same time, the 2-liquid enhanced reactor is set at the top and connected to the 8-raw material premixer to play a secondary mixing role. It can also increase the contact time of the gas-liquid two phases from top to bottom, which can make the reaction more uniform. Therefore, the position of the 2-liquid enhanced reaction device is fixed. A 3-gas enhanced reactor is provided at the inner bottom of the 1-reaction tank, and a pipeline is provided at the outer bottom of the 1-reaction tank, which is directly connected to the 3-gas enhanced reactor through a pipeline. At the same time, a 23-delivery pump 3 is provided on the pipeline for passing air into the 3-gas enhanced reactor. After the air enters the 3-gas enhanced reactor, it is fully crushed and fully reacts with the atomized raw materials.

[0039] After sufficient reaction, the material is transported to the 4-flash tank via the 25-transfer pump 5. While providing power to the material, the 25-transfer pump 5 can also defoam the material, facilitating the next step of the reaction process. The top of the 4-flash tank is provided with a pipeline connected to the middle of the side wall of the 5-product separation tower. The pipeline is provided with a 26-transfer pump 6. The bottom of the 4-flash tank is provided with a pipeline, one end of which is connected to the bottom of the flash tank and the other end is connected to the mixing pipeline through the 10-liquid mixer 1, and then re-enters the 1-reaction tank. The pipeline is connected to the 1-reaction tank and is provided with a 24-transfer pump 4 in the pipeline section before entering the 10-liquid mixer 1 to provide power to the material. The above two pipelines form the 34-first circulation pipeline. When the material enters the 4-flash tank, the temperature inside the 4-flash tank varies between 100°C and 160°C, and the pressure varies between 0.5 atm and 2 atm. The 4-flash tank rapidly vaporizes and separates the material into vapor and liquid phases. The separated vapor phase is transported from the top of the 4-flash tank via the 26-delivery pump 6, passing through the middle of the 5-product separation tower and entering the 5-product separation tower. The separated liquid phase is transported from the bottom of the 4-flash tank via the 24-delivery pump 4 to the 10-liquid mixer 1 for mixing, and then re-enters the 1-reaction tank through the mixing pipeline for a cyclic reaction. The 34-first circulation pipeline completes the first cycle, continuously returning the liquid phase material to the 1-reaction tank for continuous reaction and utilization.

[0040] When the vapor phase material enters the 5-product separation tower, the working pressure of the 5-product separation tower is 0.5 atm-1.5 atm, the reaction temperature is 55°C-105°C, the total number of plates is 26, and the reflux ratio is 5.5. The top of the 5-product separation tower is provided with a pipeline, on which are provided an 18-condenser 1, a 15-reflux tank 1 and a 30-delivery pump 10. The 18-condenser 1 and the 15-reflux tank 1 are connected in parallel and then connected in series with the 30-delivery pump 10, and then connected to the middle side wall of the 6-recovery tower through the 30-delivery pump 10; the top of the 6-recovery tower is also provided with a 19-condenser 2, a 16-reflux tank 2 and a 31-delivery pump 11. The 19-condenser 2 and the 16-reflux tank 2 are connected in parallel and then connected in series with the 31-delivery pump 11, and enter the 11-liquid mixer 2 through the 31-delivery pump and then enter the collecting pipe. The collecting pipe enters the 10-liquid mixer 1 through the 22-delivery pump 2 and then is connected to the 1-reaction tank to form a 35-second circulation pipeline. The bottom of the 5-product separation tower is directly connected to the middle of the 7-product refining tower via a pipeline. A 27-delivery pump 7 is installed on this pipeline, and a 12-reboiler 1 is also installed at the bottom of the 5-product separation tower. The bottom of the 6-recovery tower is also equipped with a 28-delivery pump 8 and a 13-reboiler 2. In the present invention, the material inlets for the 5-product separation tower, the 6-recovery tower, and the 7-product refining tower are all located in the middle of the tower body. This arrangement allows the incoming materials to undergo rapid transformation and separation / recovery / refining in the middle of the tower body, effectively improving work efficiency. It also effectively utilizes gravity and the properties of the reaction raw materials themselves to promote their entry into the next process, achieving environmental benefits and improving safety during the reaction process.

[0041] The vapor phase material generated during the reaction enters the 5-product separation tower, and the 12-reboiler 1 provides heat for the 5-product separation tower, so that the 5-product separation tower separates the vapor phase material. After separation, the light components such as water and cyclohexene that have not reacted fully are extracted from the top of the 5-separation tower, and are condensed and refluxed through the 18-condenser 1 and the 15-reflux tank 1 to become liquid again, and are powered by the 30-transfer pump 10 to enter the 6-recovery tower through the middle of the side wall of the 6-recovery tower. At this time, the temperature in the recovery tower is 120°C-230°C, the working pressure is 4.5atm-4.7atm, the total number of tower plates is 25, and the reflux ratio is 5. The 13-reboiler 2 at the bottom of the 6-recovery tower provides it with heat, while making the temperature in the 6-recovery tower higher. On the one hand, the 6-recovery tower can recover the reaction raw materials such as unreacted water or cyclohexene. On the other hand, side reactions will occur during the reaction process, and the side reactions can generate high-purity cyclohexanone. The 6-recovery tower can transfer the high-purity cyclohexanone through the 28-delivery pump 8 at the bottom of the 6-reaction tower, thereby realizing the recovery of the high-purity by-product cyclohexanone. Since the temperature in the 6-recovery tower is relatively high, the unreacted raw materials recovered may be vaporized for the second time. Therefore, a 19-condenser 2 and a 16-reflux tank 2 are set at the outlet of the top of the 6-recovery tower for secondary condensation and reflux to convert them into liquid materials, which are mixed again through the 11-liquid mixer 2 and the 10-liquid mixer 1, and re-enter the 1-reaction tank through the mixing pipeline to repeat the first cycle and the above reaction process.

[0042] The mixture of water and cyclohexene oxide generated in the 5-product separation tower can enter the inlet located in the middle of the side wall of the 7-product refining tower from the bottom of the 5-product separation tower through the 27-delivery pump 7. At this time, the temperature in the product refining tower is 100℃-150℃, the reaction pressure is 0.5atm-1.5atm, the total number of tower plates is 30, and the reflux ratio is 5.3. The top of the 7-product refining tower is provided with an outlet, and a pipeline is provided at the outlet to connect the 20-condenser 3 and the 17-reflux tank 3 in parallel. The two are connected in series with the 32-delivery pump 12. After passing through the 32-delivery pump 12, the pipeline is connected to the 11-liquid mixer 2 and merged into the collecting pipe. The collecting pipe enters the 10-liquid mixer 1 through the 22-delivery pump 2, and enters the 1-reaction tank again through the mixing pipeline to form the 36-third circulation pipeline. The bottom of the 7-product refining tower is equipped with a pipeline connected to the 29-delivery pump 9 for directly outputting the reaction product; it is also equipped with a 14-reboiler 3. After the mixture of water and cyclohexane separated by the 5-product separation tower enters the 7-product refining tower, the 14-reboiler 3 operates to provide energy for the 7-product refining tower; the 7-product refining tower refines and separates the water and cyclohexane mixture to obtain water and cyclohexane. The dehydrated cyclohexane is output through the 29-delivery pump 9 provided at the bottom of the 7-product refining tower. The separated water enters the 20-condenser 3 and the 17-reflux tank 3 for condensation and reflux, and is then input into the 11-liquid mixer 2 through the 32-delivery pump 12 for thorough mixing with the raw materials that have not been fully reacted during the second circulation process. Finally, it enters the 1-reaction tank again through the 36-third circulation pipeline for circulation.

[0043] In this utility model, each pipeline is equipped with a flow control valve. In actual use, the flow control valve can be designed and installed according to actual needs. In the flash tank, product separation tower, product refining tower, and recovery tower, the temperature at the top and bottom of the tower differ due to the tower's inherent structure, resulting in uneven temperatures during the reaction process.

[0044] In the present invention, the materials generated during the reaction are fully recycled through a circulation pipeline, achieving maximum utilization of the raw materials under catalyst-free conditions; at the same time, the recovery tower can recycle the raw materials that have not fully reacted, and the recovery tower can realize the recycling of high-purity by-products, which not only prevents the by-products from re-entering the reaction, but also effectively improves economic benefits. At the same time, through the provision of a condenser, a reboiler, a reflux tank, a gas-enhanced reactor, and a liquid-enhanced reactor, the reaction can be operated at room temperature and pressure, greatly improving safety.

[0045] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A device for continuously and gently producing cyclohexene oxide without catalyst, characterized in that: It includes a reaction tank, the inner top of which is provided with a liquid enhancement reactor, the liquid enhancement reactor is externally connected to a mixing pipeline, the mixing pipeline is formed by a first circulation pipeline, a second circulation pipeline and a third circulation pipeline being combined through a liquid mixer 1, the first circulation pipeline is used for reaction; the second circulation pipeline is used for separation and recovery; the third circulation pipeline is used for refining, and the first circulation pipeline, the second circulation pipeline and the third circulation pipeline are connected in parallel.

2. The device for continuously and gently producing cyclohexene oxide without catalyst according to claim 1, characterized in that A gas intensification reactor is provided at the inner bottom of the reaction tank, and the gas intensification reactor is directly connected to the gas delivery pump provided at the bottom of the reaction tank; a pipeline is provided on the side wall of the reaction tank to connect with the flash tank, and a pipeline is provided at the bottom of the flash tank to form a first circulation pipeline through the liquid mixer 1 and the mixing pipeline.

3. The device for continuously and gently producing cyclohexene oxide without catalyst according to claim 2, characterized in that: The inlets of the first circulation pipeline and the second circulation pipeline are connected in parallel through a flash tank. A pipeline is provided on the top of the flash tank to connect to the middle of the side wall of the product separation tower. A pipeline is provided on the top of the product separation tower to connect to the middle of the side wall of the recovery tower. A pipeline is provided at the top outlet of the recovery tower to form a collecting pipe through a liquid mixer 2. The collecting pipe merges into the mixing pipeline through the liquid mixer 1 to form the second circulation pipeline. The product separation tower and the recovery tower are connected in series.

4. The device for continuously and gently producing cyclohexene oxide without catalyst according to claim 3, characterized in that: The inlets of the second circulation pipeline and the third circulation pipeline are connected in parallel through the separation tower. A pipeline is provided at the bottom of the separation tower to connect with the middle of the side wall of the product refining tower. A pipeline is provided at the top outlet of the product refining tower to form a collecting pipe through the liquid mixer 2. The collecting pipe merges into the mixing pipeline through the liquid mixer 1 to form the third circulation pipeline.

5. The device for continuously and gently producing cyclohexene oxide without catalyst according to any one of claims 3 to 4, characterized in that: The product separation tower, recovery tower and product refining tower are all equipped with a condenser, a reboiler and a reflux tank.

6. The device for continuously and gently producing cyclohexene oxide without catalyst according to claim 1, characterized in that: The reaction device further comprises a raw material premixer, which enters the mixing pipeline through the liquid mixer 1 and is connected to the reaction tank.

7. The device for continuously and gently producing cyclohexene oxide without catalyst according to claim 6, characterized in that: The raw material premixer is directly connected to the raw material storage tank, and a stirring paddle is provided inside the raw material premixer, and the stirring paddle is located at 1 / 3-1 / 2 of the distance from the bottom of the raw material premixer.

8. The device for continuously and gently producing cyclohexene oxide without catalyst according to claim 5, characterized in that: The product separation tower, recovery tower and product refining tower are all provided with tower plates. The total number of tower plates of the product separation tower is 15-30; the total number of tower plates of the recovery tower is 15-35; and the total number of tower plates of the product refining tower is 20-40.

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