WO2021208199A1 - 一种氨肟化兼回收叔丁醇的反应系统及方法 - Google Patents

一种氨肟化兼回收叔丁醇的反应系统及方法 Download PDF

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WO2021208199A1
WO2021208199A1 PCT/CN2020/092774 CN2020092774W WO2021208199A1 WO 2021208199 A1 WO2021208199 A1 WO 2021208199A1 CN 2020092774 W CN2020092774 W CN 2020092774W WO 2021208199 A1 WO2021208199 A1 WO 2021208199A1
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tert
butanol
reaction
recovery
oximation
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PCT/CN2020/092774
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English (en)
French (fr)
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张志炳
周政
张锋
李磊
孟为民
王宝荣
杨高东
罗华勋
杨国强
田洪舟
曹宇
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南京延长反应技术研究院有限公司
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Publication of WO2021208199A1 publication Critical patent/WO2021208199A1/zh

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation

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  • the invention belongs to the technical field of enhanced reactions, and specifically relates to a reaction system and method for ammoximation and recovery of tert-butanol.
  • Caprolactam is an important organic compound, and its downstream products are widely used in industries such as spinning, tires, and food packaging.
  • the production process mostly uses ammoximation to produce cyclohexanone oxime, and then undergoes liquid phase rearrangement to generate caprolactam.
  • the cyclohexanone ammoximation reaction is the core control program in this process.
  • the main factors affecting the reaction are mass transfer efficiency, reaction temperature and pressure, reaction time, catalyst concentration, raw material ratio, etc. After research, it is found that the mass transfer efficiency and reaction temperature and pressure have a great impact on production.
  • the gas-liquid phase mass transfer area of the existing oximation reactor is limited, and the gas-liquid phase boundary area formed in the reactor is small, resulting in insufficient mass transfer space, and the reaction mixture raw materials and ammonia cannot be fully mixed, resulting in insufficient mass transfer space.
  • the reaction time is too long, the oximation conversion rate is low, which increases the occurrence of side reactions; on the other hand, the oximation reaction is a strong exothermic reaction, and the temperature and pressure are too high, which increases the decomposition products of cyclohexanone and cyclohexanone oxime These products are not easy to be removed in the later process, which affects the yield and quality of the final product caprolactam.
  • the first object of the present invention is to provide a reaction system for ammoximation and recovery of tert-butanol.
  • the reaction system is equipped with a micro-interface generator inside the ammoximation reactor. After the micro-interface generator is installed, On the one hand, the ammonia gas can be dispersed and broken into micro bubbles with a diameter of micrometers, and the phase boundary area between the ammonia gas and the liquid phase material can be increased, so that the mass transfer space is fully satisfied, and the residence time of the ammonia gas in the liquid phase is increased.
  • the second object of the present invention is to provide a method for reaction using the above reaction system, which has milder operating conditions, reduces the temperature and pressure of the oximation reaction while ensuring the reaction efficiency, and has high safety performance and energy consumption. Low, achieving a better reaction effect than the existing process.
  • the invention provides a reaction system for ammoximation and recovery of tert-butanol, which is characterized by comprising an oximation reactor, a reaction clear liquid buffer tank, a tail gas absorption tower, a tert-butanol recovery tower and a tert-butanol reflux tank, in,
  • the top of the oximation reactor is provided with a tail gas outlet
  • the bottom of the oximation reactor is provided with a discharge port
  • the discharge port is connected to the reaction clear liquid buffer tank
  • the tail gas outlet is connected to the tail gas.
  • the absorption tower is connected, the material from the reaction clear liquid buffer tank is passed through the middle section of the tert-butanol recovery tower for the recovery of tert-butanol, and the top of the tert-butanol recovery tower is connected to the tert-butanol.
  • Reflux tank is connected for gas-liquid separation;
  • An external circulation heat exchange device is arranged outside the oximation reactor to control the temperature inside the oximation reactor; a micro-interface generator is arranged inside the oximation reactor to disperse the crushed gas into a diameter of Micron-level micro-bubbles.
  • the cyclohexanone ammoximation reaction has the following problems: On the one hand, the gas-liquid mass transfer area of the existing oximation reactor is limited. The conversion of cyclohexanone is incomplete, and the conversion rate of oximation is low, which increases the occurrence of side reactions; on the other hand, the ammoximation reaction is a strong exothermic reaction, and the temperature is too high, which increases the content of cyclohexanone and cyclohexanone oxime. Decomposition products, these products are not easily removed in the subsequent process, which affects the yield and quality of the final product caprolactam.
  • the reaction system for ammoximation and recovery of tert-butanol according to the present invention can disperse and break the ammonia gas into micro-sized micro-bubbles with a diameter of micrometers, and increase the ammonia gas and liquid phase after a micro-interface generator is installed inside the oximation reactor.
  • the phase boundary area between the materials makes the mass transfer space fully satisfied, and increases the residence time of ammonia in the liquid phase, reduces the consumption of ammonia, thereby greatly improving the efficiency of the oximation reaction, effectively inhibiting side reactions, and significantly Reduce the energy consumption of the reaction process; on the other hand, it reduces the reaction temperature and pressure, reduces the decomposition products of cyclohexanone and cyclohexanone oxime, improves the yield and quality of the final product caprolactam, and reduces energy consumption and improves the system safety.
  • the side wall of the oximation reactor is provided with an air inlet for introducing raw ammonia gas, the air inlet extends to the inside of the micro-interface generator through a pipe, and the micro-interface generator
  • the type is a pneumatic micro-interface generator, the number of the micro-interface generator is more than one, and each of the micro-interface generators is connected in parallel with each other.
  • the ammonia gas is fed into the pneumatic micro-interface generator to disperse and break into micron-level micro-bubbles, which effectively increases the mass transfer area between the ammonia gas and the liquid phase material, reduces the mass transfer resistance, and improves the reaction efficiency.
  • a plurality of the micro-interface generators can also be arranged in the oximation reactor in a series connection or a series-parallel hybrid connection. More preferably, the micro-interface generator is connected to a pipe by welding, thread or flange, and the pipe is fixed inside the oximation reactor.
  • the structure of the micro-interface generator belongs to the prior art, so the specific structure of the micro-interface generator is not the protection focus of the present invention.
  • the middle section of the tert-butanol recovery tower is respectively provided with a liquid inlet and a gas inlet, the liquid inlet is connected to the bottom of the reaction clear liquid buffer tank; the gas inlet is connected to the top of the reaction clear liquid buffer tank connect.
  • the liquid in the reaction clear liquid buffer tank enters the tert-butanol recovery tower from the liquid inlet, and the gas in the reaction clear liquid buffer tank enters the tert-butanol recovery tower from the gas inlet.
  • the gas inlet and the liquid inlet are changed because the material composition in the reaction clear liquid buffer tank is more complicated.
  • Most of the tert-butanol exists in liquid form, and a small amount of it exists in the reaction product in gaseous form. This way, the gas inlet and liquid inlet are set up.
  • the dual-material imports can ensure the full recycling of tert-butanol.
  • a liquid level-flow cascade control system can be provided on the pipeline between the liquid inlet and the reaction clear liquid buffer tank.
  • the liquid level meter in the liquid level-flow cascade control system can be a pressure transmitter, and the flow meter can be a turbine flowmeter.
  • the top of the tert-butanol recovery tower is provided with a tower top condenser, and the tower kettle is provided with a tower kettle reboiler. In order to achieve a better condensation effect, two overhead condensers can be connected in series at the top of the tower.
  • the first stage overhead condenser adopts circulating cooling water for condensation
  • the second stage overhead condenser adopts chilled brine for condensation. More preferably, in order to avoid the hydrolysis of cyclohexanone oxime to cyclohexanone at high temperature, the tower kettle reboiler adopts a one-pass thermosyphon reboiler to reduce the high temperature residence time of oxime water.
  • the reaction system further includes a reflux pipeline, one end of the reflux pipeline is connected to the top of the tert-butanol recovery tower, and the other end is connected to the bottom of the tert-butanol reflux tank for removing the tertiary
  • the material in the butanol reflux tank is returned to continue separation and purification;
  • the reflux pipeline is provided with a reflux pump, and a part of the condensate is pressurized by the reflux pump and then enters the reflux pipeline as a reflux at the top of the tower for the recovery of the tert-butanol ingested
  • the excess heat at the top of the tower can maintain the heat balance of the entire tower.
  • the recovery purity of tert-butanol can also be improved.
  • the reflux pump can be used to adjust the reflux, so that the reflux is stable and the operability is good.
  • a pipe connecting the tail gas outlet and the tail gas absorption tower is provided with an exhaust gas cooler
  • the tert-butanol reflux tank is provided with a non-condensable gas outlet
  • the non-condensable gas outlet is connected to the exhaust gas
  • the cooler makes the non-condensable gas mixed with the tail gas enter the tail gas absorption tower for recycling.
  • the exhaust gas cooler By setting the exhaust gas cooler, the non-condensable gas can be cooled, which improves the utilization rate of on-site tail gas recovery and saves energy.
  • vaporized from the top of the tert-butanol recovery tower will enter the tert-butanol reflux tank after being cooled by the condenser at the top of the tower, and the non-condensable gas that has not cooled down through the exhaust gas cooler After being mixed with tail gas, it enters the tail gas absorption tower for ammonia recovery and utilization.
  • the type of the tert-butanol recovery tower is a vertical sieve tray tower.
  • Impurities in the circulating tert-butanol include cyclohexanone, cyclohexanol, cyclohexanone oxime, etc.
  • the boiling point of this part of the impurities is much higher than that of tert-butanol, so it is easier to separate; but there are some impurities whose boiling point is close to that of tert-butanol. It is more difficult.
  • the t-butanol recovery tower provided by the present invention adopts a vertical sieve tray tower, which has the characteristics of high mass transfer space utilization and good mass transfer effect, which can effectively solve the problem of difficult separation of light impurities of t-butanol, and In the operation, a reasonable reflux ratio and a reasonable feeding position are adopted to improve the removal efficiency of tert-butanol light impurities.
  • the inner bottom end of the tert-butanol recovery tower is set in the shape of a cone, which can ensure that only the recovered tert-butanol is received, and this setting mode can make cyclohexanone oxime and tert-butanol better Separation, thereby improving the recovery efficiency of tert-butanol, and improving the purity of tert-butanol at the same time.
  • the reaction system further includes a circulating tert-butanol tank, the top of the circulating tert-butanol tank is connected to the bottom of the tert-butanol reflux tank, and the bottom of the circulating tert-butanol tank is connected to the oximation tank.
  • the bottom of the reactor is connected so that tert-butanol can be reused as a reaction solvent.
  • a small part of the condensate in the tert-butanol reflux tank is used for reflux at the top of the tower, and most of the remaining part is recycled into the oximation reactor through the circulating tert-butanol tank to be reused as a reaction solvent, which reduces the use cost of tert-butanol.
  • the tert-butanol tank can be set to automatically spray condensed water, so that the temperature in the tank can be kept constant.
  • the present invention also provides a method for oximation reaction and recovery of tert-butanol, including the following steps:
  • the ammonia gas After the ammonia gas is dispersed and broken into micro-bubbles, it undergoes a catalytic oximation reaction with the liquid phase materials; in the process of the catalytic oximation reaction, the unreacted gas is recycled for use in the tail gas, and the reaction product is collected in a clear liquid manner, and The tert-butanol in the reaction product is recovered.
  • liquid phase materials including cyclohexanone, hydrogen peroxide and tert-butanol
  • ammonia gas is introduced into the micro-interface generator set inside the oximation reactor to make it
  • the ammonia gas is broken into micro-bubbles with a diameter of micrometers. After being dispersed and broken into micro-bubbles, the ammonia gas undergoes a catalytic oximation reaction with the liquid phase materials.
  • the unreacted gas undergoes tail gas recovery and utilization.
  • the reaction product is collected as a clear liquid, it enters the reaction clear liquid buffer tank through the discharge port, and then passes through the tert-butanol recovery tower.
  • the liquid inlet and the gas inlet of the gas enter the tower, and the tert-butanol in the reaction product is recovered, and the recovered tert-butanol enters the oximation reactor again to be reused as a reaction solvent.
  • the temperature of the oximation reaction is 80-82° C., and the pressure is 0.18-0.23 MPa.
  • the present invention has the following beneficial effects:
  • the present invention can disperse and break the ammonia gas into micro-sized micro-bubbles with a diameter of micrometers by installing a micro-interface generator inside the oximation reactor, increase the phase boundary area between the ammonia gas and the liquid phase material, and make the mass transfer space Fully satisfy, and increase the residence time of ammonia in the liquid phase, reduce the consumption of ammonia, thereby greatly improving the efficiency of the oximation reaction, effectively inhibiting side reactions, and significantly reducing the energy consumption of the reaction process; on the other hand, it reduces The reaction temperature and pressure reduce the decomposition products of cyclohexanone and cyclohexanone oxime, increase the yield and quality of the final product caprolactam, reduce energy consumption, and improve system safety.
  • Fig. 1 is a schematic structural diagram of a reaction system for ammoximation and recovery of tert-butanol provided by an embodiment of the present invention.
  • the reaction system for ammoximation and recovery of tert-butanol in an embodiment of the present invention includes an oximation reactor 10, a reaction clear liquid buffer tank 20, a tail gas absorption tower 30, a tert-butanol recovery tower 40 and In the tert-butanol reflux tank 50, the oximation reactor 10 is provided with a micro-interface generator 60 for dispersing the crushed gas into micro-bubbles with a diameter of micrometers.
  • the side wall of the oximation reactor 10 is provided with an air inlet 13 for introducing raw ammonia gas, the air inlet 13 extends through a pipe to the inside of the micro interface generator 60, and the ammonia gas passes into the micro interface generator 60.
  • the inside of the oximation reactor 10 is dispersed and broken into micro-sized micro-bubbles, which are fully emulsified with the liquid phase material in the oximation reactor 10 and then undergo ammoximation reaction, which effectively increases the mass transfer area between the ammonia gas and the liquid phase material. Reduce mass transfer resistance and improve reaction efficiency.
  • the type of the micro-interface generator 60 is a pneumatic micro-interface generator, which is driven by ammonia gas. It can be understood that the number of micro-interface generators 60 in this embodiment is not limited. In order to increase the dispersion and mass transfer effects, additional micro-interface generators can also be added. Multiple micro-interface generators can be connected in series or in parallel. Or a series-parallel hybrid connection is arranged inside the oximation reactor.
  • the ammoximation reaction is a strong exothermic reaction.
  • the normal oximation reaction does not require any external heating.
  • the reaction heat can maintain the heat required in the continuous reaction process.
  • An external circulation device is provided to control the temperature during the reaction process.
  • the external circulation device includes a circulation pipe.
  • the circulation pipe is equipped with a fully-automatically adjusted condenser 70.
  • the fully-automatically adjusted condenser 70 can quickly and automatically cool the circulating materials.
  • the circulating pipe A circulating pump 80 is provided on the upper side.
  • the circulating pump 80 can be vertical or horizontal, and the number of pump bodies is not limited, and one or more of them can be installed in series or in parallel to increase the circulating power.
  • the top of the oximation reactor 10 of this embodiment is provided with a tail gas outlet 11, and the tail gas outlet 11 is connected to the tail gas absorption tower 30. During the reaction process, unreacted gas enters the tail gas absorption tower 30 from the tail gas outlet 11 for recycling.
  • an absorption liquid outlet 31 is also provided at the bottom of the tail gas absorption tower 30, and the absorption liquid outlet 31 is connected to the top of the oximation reactor 10 for the absorption liquid to return to the inside of the reactor for reuse.
  • the bottom of the oximation reactor 10 is provided with a discharge port 12, and the discharge port 12 is connected to the reaction clear liquid buffer tank 20.
  • the discharge port 12 is connected to the reaction clear liquid buffer tank 20.
  • it can be provided on the connecting pipe between the reaction clear liquid buffer tank 20 and the discharge port 12
  • the external filtering device 90 prevents the catalyst from entering the reaction clear liquid buffer tank 20 after the internal filter of the oximation reactor 10 is blocked.
  • the material from the reaction clear liquid buffer tank 20 is passed through the middle section of the tert-butanol recovery tower 40 for the recovery of tert-butanol, and the top of the tert-butanol recovery tower 40 is connected to the tert-butanol reflux tank 50 for Gas-liquid separation.
  • the middle section of the tert-butanol recovery tower 40 is respectively provided with a liquid inlet 41 and a gas inlet 42.
  • the liquid inlet 41 is connected to the bottom of the reaction clear liquid buffer tank 20; the gas inlet 42 is connected to the top of the reaction clear liquid buffer tank 20,
  • the gas inlet and the liquid inlet are set up at the same time because the material composition in the reaction clear liquid buffer tank is relatively complicated.
  • Most of the tert-butanol exists in liquid form, and a small amount of it exists in the reaction product in gaseous form, so the gas inlet is set up.
  • the dual material inlet with the liquid inlet can ensure the full recovery and utilization of tert-butanol.
  • the tert-butanol recovery tower 40 is a vertical sieve tray, which has the characteristics of high mass transfer space utilization and good mass transfer effect, which can effectively solve the problem of difficult separation of light impurities of tert-butanol, and In the operation, a reasonable reflux ratio and a reasonable feeding position are adopted to improve the removal efficiency of t-butanol light impurities.
  • the inner bottom end of the t-butanol recovery tower 40 is set in the shape of a cone, which can ensure that only The recovered tert-butanol is received, and this setting mode can better separate cyclohexanone oxime and tert-butanol, thereby improving the recovery efficiency of tert-butanol and improving the purity of tert-butanol at the same time.
  • a reflux pipeline is arranged between the tert-butanol recovery tower 40 and the tert-butanol reflux tank 50, one end of the return pipeline is connected to the top of the tert-butanol recovery tower 40, and the other end is connected to the bottom of the tert-butanol reflux tank 50 It is connected to return the substance in the tert-butanol reflux tank 50 to continue separation and purification.
  • a reflux pump 120 is provided on the reflux pipeline. A part of the condensate is pressurized by the reflux pump 120 and then enters the reflux pipeline as a reflux at the top of the tower.
  • the reflux pump 120 can be used to adjust the reflux, so that the reflux is stable and the operability is good.
  • the top of the tert-butanol recovery tower 40 is provided with a top condenser 100, and the bottom of the tower is provided with a bottom reboiler 110, and the material from the top condenser 100 of the tert-butanol recovery tower 40 flows first. After passing through the tert-butanol reflux tank 50, it returns to the top of the tower.
  • two overhead condensers 100 are connected in series at the top of the tower.
  • the first stage overhead condenser adopts circulating cooling water for condensation
  • the second stage overhead condenser adopts chilled brine for condensation.
  • the tower kettle reboiler 110 adopts a one-pass thermosyphon reboiler to reduce the high temperature residence time of oxime water.
  • the pipe connecting the tail gas outlet 11 and the tail gas absorption tower 30 is provided with an exhaust gas cooler 130
  • the tert-butanol reflux tank 50 is provided with a non-condensable gas outlet 51
  • the non-condensable gas outlet 51 is connected to the exhaust gas cooler 130 to prevent The condensed gas is mixed with the tail gas and enters the tail gas absorption tower 30 for recycling.
  • the reaction system further includes a circulating tert-butanol tank 140, the top of the circulating tert-butanol tank 140 is connected to the bottom of the tert-butanol reflux tank 50, and the bottom of the circulating tert-butanol tank 140 is connected to the oximation reactor 10. Connect to the bottom of the t-butanol so that tert-butanol can be reused as a reaction solvent.
  • a small part of the condensate in the tert-butanol reflux tank 50 is refluxed at the top of the tower, and most of the remaining part is recycled into the oximation reactor 10 through the circulating tert-butanol tank 140 to be reused as a reaction solvent, thereby reducing the cost of using tert-butanol.
  • the circulating tert-butanol tank 140 can be provided with automatic spraying of condensed water, so that the temperature in the tank can be kept constant.
  • Ammonia gas first enters the micro-interface generator 60 through the air inlet 13 to be dispersed and broken into micron-level micro-bubbles.
  • the liquid phase mixed raw materials (including hydrogen peroxide, cyclohexanone, circulating tert-butanol and circulating materials, etc.) enter the oximation reaction In the vessel 10, the dispersed and crushed microbubbles and the liquid phase mixed raw materials are fully emulsified, which effectively increases the mass transfer area of the gas-liquid two-phase and reduces the mass transfer resistance.
  • the temperature in the oximation reactor 10 is 80-82° C. and the pressure is 0.18-0.23 MPa.
  • the ammoximation reaction is a strong exothermic reaction
  • the fully-automatically adjusted condenser 70 arranged on the outer circulation pipeline makes the circulating materials quickly and automatically cool down, thereby reducing the temperature inside the reactor.
  • unreacted ammonia, alcohol and other gases are cooled from the tail gas outlet 11 through the exhaust gas cooler 130 and then enter the tail gas absorption tower 30.
  • the tail gas absorption tower 30 uses desalinated water to absorb the ammonia and alcohol. After the absorption liquid exits the absorption liquid outlet 31, it enters the oximation reactor 10 for repeated recycling.
  • the oximation reaction products (cyclohexanone oxime, ammonia and a small amount of tert-butanol, etc.) enter the reaction clear liquid buffer tank 20 through the discharge port 12 in a clear liquid manner, and then respectively pass through the liquid inlet 41 of the tert-butanol recovery tower 40.
  • the gas inlet 42 enters the tower to recover the tert-butanol.
  • the mixed fraction of water, ammonia, and tert-butanol steamed from the top of the tert-butanol recovery tower 40 is cooled by the top condenser 100 and then enters the tert-butanol.
  • the uncooled non-condensable gas passes through the non-condensable gas outlet 51, passes through the exhaust gas cooler 130, is mixed with the tail gas of the oximation reactor 10, and then enters the tail gas absorption tower 30 for ammonia recovery.
  • a small part of the condensate in the tert-butanol reflux tank 50 is pressurized by the reflux pump 120 and refluxed as the top of the tower. The cost of using tert-butanol.

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Abstract

本发明提供了一种氨肟化兼回收叔丁醇的反应系统及方法，包括肟化反应器、反应清液缓冲罐、尾气吸收塔、叔丁醇回收塔和叔丁醇回流罐，其中，肟化反应器的顶部设置有尾气出口，肟化反应器的底部设置有出料口，出料口与所述反应清液缓冲罐连接，尾气出口与所述尾气吸收塔连接，反应清液缓冲罐出来的物料从叔丁醇回收塔的中段通入，叔丁醇回收塔的顶部与叔丁醇回流罐连接，肟化反应器外部设置有外循环换热装置，内部设置有微界面发生器，用于分散破碎气体。本发明的氨肟化兼回收叔丁醇的反应系统，通过在反应器内部设置了微界面发生器后，增大了气液相的传质面积，降低了反应温度和压力，从而抑制了副反应的发生，提高了肟化反应效率。

Description

一种氨肟化兼回收叔丁醇的反应系统及方法 技术领域
本发明属于强化反应技术领域，具体涉及一种氨肟化兼回收叔丁醇的反应系统及方法。
背景技术
己内酰胺是一种重要的有机化合物，其下游产品广泛应用于纺丝、轮胎、食品包装等行业。生产工艺多采用氨肟化生产环己酮肟，然后再进行液相重排生成己内酰胺，环己酮氨肟化反应是该工艺中的核心控制程序。在环己酮氨肟化反应过程中，影响反应的因素主要有传质效率、反应温度压力、反应时间、催化剂浓度原料配比等，经研究发现，传质效率和反应温度压力对生产影响甚大，一方面，现有肟化反应器的气液相传质面积有限，反应器内形成的气液相界面积较小，导致传质空间不足，反应混合原料和氨气无法得到充分混合，造成反应时间过长，肟化转化率低下，加大了副反应的发生；另一方面，肟化反应是强放热反应，温度压力太高，增加了环己酮、环己酮肟的分解产物，这些产物在后工序中不易被除去，影响了最终产物已内酰胺的产量和质量。
综上所述，为提高肟化反应效率，降低反应温度压力，减少副反应的发生，对氨肟化工业化装置进行改进，是降低氨肟化成本、提升氨肟化生产负荷急需解决的问题。
发明内容
鉴于此，本发明的第一目的在于提供一种氨肟化兼回收叔丁醇的反应系统，该反应系统在氨肟化反应器内部设置微界面发生器，通过设置了微界面发 生器后，一方面可以将氨气分散破碎成直径微米级的微气泡，增加氨气和液相物料之间的相界面积，使得传质空间充分满足，而且增加了氨气在液相中的停留时间，降低了氨气的耗量，从而大幅提高肟化反应效率、有效抑制副反应、显著降低反应过程的能耗；另一方面降低了反应温度以及压力，减少了环己酮和环己酮肟的分解产物，提高了最终产物己内酰胺的产量和质量，而且减少了能耗，提高了系统安全性。
本发明的第二目的在于提供一种采用上述反应系统进行反应的方法，该方法的操作条件更加温和，在保证反应效率的同时降低了肟化反应的温度和压力，而且安全性能高、能耗低，达到了比现有工艺更佳的反应效果。
为了实现本发明的上述目的，特采用以下技术方案：
本发明提供了一种氨肟化兼回收叔丁醇的反应系统，其特征在于，包括肟化反应器、反应清液缓冲罐、尾气吸收塔、叔丁醇回收塔和叔丁醇回流罐，其中，
所述肟化反应器的顶部设置有尾气出口，所述肟化反应器的底部设置有出料口，所述出料口与所述反应清液缓冲罐连接，所述尾气出口与所述尾气吸收塔连接，所述反应清液缓冲罐出来的物料从所述叔丁醇回收塔的中段通入以用于叔丁醇的回收，所述叔丁醇回收塔的顶部与所述叔丁醇回流罐连接以用于气液分离；
所述肟化反应器外部设置有外循环换热装置，用于控制所述肟化反应器内部的温度；所述肟化反应器内部设置有微界面发生器，用于分散破碎气体成直径为微米级别的微气泡。
现有技术中，环己酮氨肟化反应存在以下问题：一方面，现有肟化反应器的气液相传质面积有限，反应过程中，反应混合原料和氨气无法得到充分混合，造成环己酮转化不完全，肟化转化率低下，加大了副反应的发生；另一方面，氨肟化反应是强放热反应，温度太高，增加了环己酮、环己酮肟的分解产物，这些产物在后工序中不易被除去，影响了最终产物已内酰胺的产量和质量。本 发明的氨肟化兼回收叔丁醇的反应系统通过在肟化反应器内部设置微界面发生器后，一方面可以将氨气分散破碎成直径微米级的微气泡，增加氨气和液相物料之间的相界面积，使得传质空间充分满足，而且增加了氨气在液相中的停留时间，降低了氨气的耗量，从而大幅提高肟化反应效率、有效抑制副反应、显著降低反应过程的能耗；另一方面降低了反应温度以及压力，减少了环己酮和环己酮肟的分解产物，提高了最终产物己内酰胺的产量和质量，而且减少了能耗，提高了系统安全性。
进一步的，所述肟化反应器的侧壁设置有用于通入原料氨气的进气口，所述进气口通过管道延伸至所述微界面发生器的内部，所述微界面发生器的类型为气动式微界面发生器，所述微界面发生器的个数为一个以上，每个所述微界面发生器之间互相并联。氨气通入气动式微界面发生器的内部分散破碎成微米级别的微气泡，有效的增大了氨气与液相物料之间的传质面积，降低传质阻力，提高反应效率。此外，多个所述微界面发生器还可通过串联方式或者串并联混合连接方式设置在所述肟化反应器的内部。更优选地，所述微界面发生器通过焊接、螺纹或者法兰连接管道，所述管道固定在所述肟化反应器的内部。另外，该微界面发生器的本身结构属于现有技术，因此其微界面发生器的具体结构并不是本发明的保护重点。
进一步的，所述叔丁醇回收塔中段分别设置有液体进口以及气体进口，所述液体进口与所述反应清液缓冲罐的底部连接；所述气体进口与所述反应清液缓冲罐的顶部连接。所述反应清液缓冲罐中的液体从所述液体进口进入叔丁醇回收塔中，所述反应清液缓冲罐中的气体从所述气体进口进入叔丁醇回收塔中，之所以同时设置了气体进口与液体进口，是因为反应清液缓冲罐中的物质成分比较复杂，叔丁醇大部分以液态形式存在，少量的以气态形式存在于反应产物中，这样设置气体进口与液体进口的双物料进口，能够保证叔丁醇的充分回收利用。
优选地，在所述液体进口与所述反应清液缓冲罐之间的管线上可设置有液 位-流量串级控制系统，相比简单的单回路控制，液位-流量串级控制系统只需利用常规的仪表即可实现更好的控制效果，液位-流量串级控制系统中的液位仪表可选压力变送器，流量仪表可选涡轮流量计。进一步的，所述叔丁醇回收塔的塔顶设置有塔顶冷凝器，塔釜设置有塔釜再沸器。为了达到更好的冷凝效果，可以在塔顶串联两个塔顶冷凝器，第一级塔顶冷凝器采用循环冷却水冷凝，第二级塔顶冷凝器采用冷冻盐水冷凝。更优选地，为避免环己酮肟在高温下水解成环己酮，所述塔釜再沸器采用一次通过式热虹吸再沸器，以减少肟水的高温停留时间。
进一步的，所述反应系统还包括回流管路，所述回流管路的一端与所述叔丁醇回收塔的顶部连接，另一端与所述叔丁醇回流罐的底部连接以用于将叔丁醇回流罐中的物质返回继续分离纯化；所述回流管路上设置有回流泵，一部分冷凝液经过回流泵加压后进入回流管路作为塔顶回流，以用于摄取所述叔丁醇回收塔顶多余热量，维持全塔热平衡，经过多次回流，还可以提高叔丁醇的回收纯度。相比自然回流，采用回流泵可调节回流量，使得回流量稳定，操作性好。
进一步的，所述尾气出口和所述尾气吸收塔连接的管道上设置有排放气冷却器，所述叔丁醇回流罐上设置有不凝气出口，所述不凝气出口连接所述排放气冷却器，使不凝气与尾气混合后进入所述尾气吸收塔进行回收利用。通过设置排放气冷却器可对不凝气体进行冷却，提高了现场尾气回收的利用率，节省了能源。叔丁醇回收塔塔顶蒸出的含水、氨、叔丁醇等的混合馏份，经过塔顶冷凝器冷却后进入叔丁醇回流罐，中间未冷却下来的不凝气体通过排放气冷却器与尾气混合后进入尾气吸收塔中进行氨回收利用。
进一步的，所述叔丁醇回收塔的类型为垂直筛板塔。循环叔丁醇内杂质有环己酮、环己醇、环己酮肟等，这一部分杂质沸点比叔丁醇高很多，所以分离较为容易；但是有部分杂质沸点与叔丁醇接近的，分离就比较困难，本发明提供的叔丁醇回收塔采用垂直筛板塔，具有传质空间利用率高，传质效果好的特 点，可以有效的解决叔丁醇轻杂分离难度大的问题，并且在操作中采取合理的回流比及合理的进料位置以提高叔丁醇轻杂的脱除效率。
进一步地，所述叔丁醇回收塔的内部底端设置成锥斗的形状，这样能保证只接收回收的叔丁醇，并且该种设置方式能使环己酮肟与叔丁醇更好的分离，从而提高叔丁醇的回收效率，同时提高叔丁醇的纯度。
进一步的，所述反应系统还包括循环叔丁醇罐，所述循环叔丁醇罐的顶部与所述叔丁醇回流罐的底部连接，所述循环叔丁醇罐的底部与所述肟化反应器的底部连接，以使叔丁醇重新作为反应溶剂利用。叔丁醇回流罐中的冷凝液一小部分作为塔顶回流，其余大部分通过循环叔丁醇罐进入肟化反应器中重新作为反应溶剂利用，降低了叔丁醇的使用成本，所述循环叔丁醇罐可设置自动喷淋冷凝水，这样可使罐内温度保持恒定。
除此之外，本发明还提供了一种肟化反应兼回收叔丁醇的方法，包括如下步骤：
氨气经过分散破碎成微气泡后，与液相物料进行催化肟化反应；进行所述催化肟化反应过程中，未反应完全的气体进行尾气回收利用，反应产物以清液方式收集后，并对所述反应产物中的叔丁醇进行回收。
进一步地，先将液相物料(包括环己酮、双氧水和叔丁醇)通入肟化反应器内部，同时将氨气通入设置在肟化反应器内部的微界面发生器内，使其破碎成直径为微米级别的微气泡，氨气经过分散破碎成微气泡后，与液相物料进行催化肟化反应。
进行所述催化肟化反应过程中，未反应完全的气体进行尾气回收利用，反应产物以清液方式收集后，通过出料口进入到反应清液缓冲罐中，随后分别通过叔丁醇回收塔的液体进口和气体进口进入到塔内，并对所述反应产物中的叔丁醇进行回收，回收后的叔丁醇再次进入所述肟化反应器内部重新作为反应溶剂利用。
进一步的，所述肟化反应的温度为80-82℃，压力为0.18-0.23MPa。
与现有技术相比，本发明的有益效果在于：
本发明通过在肟化反应器内部设置微界面发生器后，一方面可以将氨气分散破碎成直径微米级的微气泡，增加氨气和液相物料之间的相界面积，使得传质空间充分满足，而且增加了氨气在液相中的停留时间，降低了氨气的耗量，从而大幅提高肟化反应效率、有效抑制副反应、显著降低反应过程的能耗；另一方面降低了反应温度以及压力，减少了环己酮和环己酮肟的分解产物，提高了最终产物己内酰胺的产量和质量，而且减少了能耗，提高了系统安全性。
附图说明
通过阅读下文优选实施方式的详细描述，各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的，而并不认为是对本发明的限制。而且在整个附图中，用相同的参考符号表示相同的部件。在附图中：
图1为本发明实施例提供的氨肟化兼回收叔丁醇的反应系统的结构示意图。
附图说明：
10-肟化反应器；                            11-尾气出口；
12-出料口；                                13-进气口；
20-反应清液缓冲罐；                        30-尾气吸收塔；
31-吸收液出口；                            40-叔丁醇回收塔；
41-液体进口；                              42-气体进口；
50-叔丁醇回流罐；                          51-不凝气出口；
60-微界面发生器；                          70-全自动调节冷凝器；
80-循环泵；                                90-外过滤装置；
100-塔顶冷凝器；                           110-塔釜再沸器；
120-回流泵；                               130-排放气冷却器；
140-循环叔丁醇罐。
具体实施方式
下面将结合附图和具体实施方式对本发明的技术方案进行清楚、完整地描述，但是本领域技术人员将会理解，下列所描述的实施例是本发明一部分实施例，而不是全部的实施例，仅用于说明本发明，而不应视为限制本发明的范围。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
在本发明的描述中，需要说明的是，术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。此外，术语“第一”、“第二”、“第三”仅用于描述目的，而不能理解为指示或暗示相对重要性。
在本发明的描述中，需要说明的是，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以具体情况理解上述术语在本发明中的具体含义。
为了更加清晰的对本发明中的技术方案进行阐述，下面以具体实施例的形式进行说明。
实施例
参阅图1所示，为本发明实施例的氨肟化兼回收叔丁醇的反应系统，包括 肟化反应器10、反应清液缓冲罐20、尾气吸收塔30、叔丁醇回收塔40和叔丁醇回流罐50，肟化反应器10内部设置有微界面发生器60，用于分散破碎气体成直径为微米级别的微气泡。具体而言，肟化反应器10的侧壁设置有用于通入原料氨气的进气口13，进气口13通过管道延伸至微界面发生器60的内部，氨气通入微界面发生器60的内部分散破碎成微米级别的微气泡，与肟化反应器10内部的液相物料充分乳化后进行氨肟化反应，这样有效的增大了氨气与液相物料之间的传质面积，降低传质阻力，提高反应效率。在本实施例中，微界面发生器60的类型为气动式微界面发生器，以氨气作为动力驱动。可以理解的是，该实施例的微界面发生器60并不局限于个数，为了增加分散、传质效果，也可以多增设额外的微界面发生器，多个微界面发生器通过串联或并联或串并联混合连接的方式设置在所述肟化反应器的内部。
其中，氨肟化反应为强放热反应，正常肟化反应不需任何外加热量，反应热能维持连续反应过程中需要的热量，多余的热能造成反应器内部物料升温，通过在肟化反应器10外部设置外循环装置来控制反应过程中的温度，外循环装置包括循环管道，循环管道上布设有全自动调节冷凝器70，全自动调节冷凝器70可以使循环物料迅速自动降温，另外，循环管道上设置有循环泵80，本实施例中，循环泵80可以是立式或者卧式，泵体个数不限，可以一个或者多个串联或并联安装来增加循环动力。
该实施例的肟化反应器10的顶部设置有尾气出口11，尾气出口11与尾气吸收塔30连接，反应过程中，未反应完全的气体从尾气出口11进入尾气吸收塔30中进行回收利用，此外，尾气吸收塔30底部还设置有吸收液出口31，吸收液出口31连接肟化反应器10顶部以用于吸收液回到反应器内部重复利用。
肟化反应器10的底部设置有出料口12，出料口12与反应清液缓冲罐20连接，作为优选，可以在反应清液缓冲罐20与出料口12之间的连接管道上设置外过滤装置90，防止肟化反应器10内部过滤器发生堵塞后催化剂进入反应清液缓冲罐20中。反应清液缓冲罐20出来的物料从叔丁醇回收塔40的中段 通入以用于叔丁醇的回收，叔丁醇回收塔40的顶部与所述叔丁醇回流罐50连接以用于气液分离。具体而言，叔丁醇回收塔40中段分别设置有液体进口41以及气体进口42，液体进口41与反应清液缓冲罐20的底部连接；气体进口42与反应清液缓冲罐20的顶部连接，之所以同时设置了气体进口与液体进口，是因为反应清液缓冲罐中的物质成分比较复杂，叔丁醇大部分以液态形式存在，少量的以气态形式存在于反应产物中，这样设置气体进口与液体进口的双物料进口，能够保证叔丁醇的充分回收利用。本实施例中，叔丁醇回收塔40为垂直筛板塔，其具有传质空间利用率高，传质效果好的特点，可以有效的解决叔丁醇轻杂分离难度大的问题，并且在操作中采取合理的回流比及合理的进料位置以提高叔丁醇轻杂的脱除效率，更优选地，叔丁醇回收塔40的内部底端设置成锥斗的形状，这样能保证只接收回收的叔丁醇，并且该种设置方式能使环己酮肟与叔丁醇更好的分离，从而提高叔丁醇的回收效率，同时提高叔丁醇的纯度。
叔丁醇回收塔40和叔丁醇回流罐50之间设置有回流管路，回流管路的一端与所述叔丁醇回收塔40的顶部连接，另一端与叔丁醇回流罐50的底部连接以用于将叔丁醇回流罐50中的物质返回继续分离提纯，回流管路上设置有回流泵120，一部分冷凝液经过回流泵120加压后进入回流管路作为塔顶回流，以用于摄取所述叔丁醇回收塔顶多余热量，维持全塔热平衡，经过多次回流，还可以提高叔丁醇的回收纯度。相比自然回流，采用回流泵120可调节回流量，使得回流量稳定，操作性好。
进一步的，叔丁醇回收塔40的塔顶设置有塔顶冷凝器100，塔釜设置有塔釜再沸器110，从叔丁醇回收塔40的塔顶泠凝器100出来的物质先流经叔丁醇回流罐50，再返回塔顶。
为了达到更好的冷凝效果，本实施例在塔顶串联两个塔顶冷凝器100，第一级塔顶冷凝器采用循环冷却水冷凝，第二级塔顶冷凝器采用冷冻盐水冷凝。更优选地，为避免环己酮肟在高温下水解成环己酮，塔釜再沸器110采用一次 通过式热虹吸再沸器，以减少肟水的高温停留时间。
此外，尾气出口11和尾气吸收塔30连接的管道上设置有排放气冷却器130，叔丁醇回流罐50设置有不凝气出口51，不凝气出口51连接排放气冷却器130，使不凝气与尾气混合后进入尾气吸收塔30进行回收利用。
本实施例中，该反应系统还包括循环叔丁醇罐140，循环叔丁醇罐140的顶部与叔丁醇回流罐50的底部连接，循环叔丁醇罐140的底部与肟化反应器10的底部连接，以使叔丁醇重新作为反应溶剂利用。叔丁醇回流罐50中的冷凝液一小部分作为塔顶回流，其余大部分通过循环叔丁醇罐140进入肟化反应器10中重新作为反应溶剂利用，降低了叔丁醇的使用成本。更优选地，循环叔丁醇罐140可设置自动喷淋冷凝水，这样可使罐内温度保持恒定。
以下简要说明本发明氨肟化兼回收叔丁醇的反应系统的工作过程和原理。
氨气通过进气口13先进入微界面发生器60内进行分散破碎成微米级别的微气泡，同时，液相混合原料(包括双氧水、环己酮、循环叔丁醇和循环物料等)进入肟化反应器10内，分散破碎后的微气泡与液相混合原料充分进行乳化，有效地增大了气液两相的传质面积，降低了传质阻力。
随着，充分乳化后的乳化液在催化剂的作用下在肟化反应器10内部进行肟化反应，肟化反应器10内的温度为80-82℃，压力为0.18-0.23MPa。其中，氨肟化反应为强放热反应，通过外循环管道上布设的全自动调节冷凝器70使循环物料迅速自动降温，从而降低了反应器内部的温度。
反应过程中，有未反应完全的氨、醇等气体从尾气出口11经过排放气冷却器130冷却后进入尾气吸收塔30中，尾气吸收塔30利用脱盐水将其中的氨和醇吸收下来成为吸收液，吸收液从吸收液出口31出来后进入肟化反应器10中进行重复回收利用。肟化反应产物(环己酮肟、氨和少量叔丁醇等)以清液方式通过出料口12进入到反应清液缓冲罐20中，随后分别通过叔丁醇回收塔40的液体进口41和气体进口42进入到塔内进行叔丁醇的回收，叔丁醇回收塔40的塔顶蒸出的含水、氨、叔丁醇的混合馏份，经过塔顶冷凝器100冷却后进 入叔丁醇回流罐50中，未冷却下来的不凝气通过不凝气出口51经过排放气冷却器130与肟化反应器10的尾气混合后进入尾气吸收塔30进行氨回收。叔丁醇回流罐50中的冷凝液其中一小部分经回流泵120加压后作为塔顶回流，其余大部分通过循环叔丁醇罐140进入肟化反应器10中重新作为反应溶剂利用，降低了叔丁醇的使用成本。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (10)

  1. 一种氨肟化兼回收叔丁醇的反应系统，其特征在于，包括肟化反应器、反应清液缓冲罐、尾气吸收塔、叔丁醇回收塔和叔丁醇回流罐，其中，
    所述肟化反应器的顶部设置有尾气出口，所述肟化反应器的底部设置有出料口，所述出料口与所述反应清液缓冲罐连接，所述尾气出口与所述尾气吸收塔连接，所述反应清液缓冲罐出来的物料从所述叔丁醇回收塔的中段通入以用于叔丁醇的回收，所述叔丁醇回收塔的顶部与所述叔丁醇回流罐连接以用于气液分离；
    所述肟化反应器外部设置有外循环换热装置，用于控制所述肟化反应器内部的温度；所述肟化反应器内部设置有微界面发生器，用于分散破碎气体成直径为微米级别的微气泡。
  2. 根据权利要求1所述的氨肟化兼回收叔丁醇的反应系统，其特征在于，所述肟化反应器的侧壁设置有用于通入原料氨气的进气口，所述进气口通过管道延伸至所述微界面发生器的内部，所述微界面发生器的类型为气动式微界面发生器，所述微界面发生器的个数为一个以上，每个所述微界面发生器之间互相并联。
  3. 根据权利要求1所述的氨肟化兼回收叔丁醇的反应系统，其特征在于，所述叔丁醇回收塔中段分别设置有液体进口以及气体进口，所述液体进口与所述反应清液缓冲罐的底部连接；所述气体进口与所述反应清液缓冲罐的顶部连接。
  4. 根据权利要求1所述的氨肟化兼回收叔丁醇的反应系统，其特征在于，所述叔丁醇回收塔的塔顶设置有塔顶冷凝器，塔釜设置有塔釜再沸器。
  5. 根据权利要求1所述的氨肟化兼回收叔丁醇的反应系统，其特征在于，所述反应系统还包括回流管路，所述回流管路的一端与所述叔丁醇回收塔的顶部连接，另一端与所述叔丁醇回流罐的底部连接以用于将叔丁醇回流罐中的物质返回继续分离纯化；所述回流管路上设置有回流泵。
  6. 根据权利要求1所述的氨肟化兼回收叔丁醇的反应系统，其特征在于，所述尾气出口和所述尾气吸收塔连接的管道上设置有排放气冷却器，所述叔丁醇回流罐上设置有不凝气出口，所述不凝气出口连接所述排放气冷却器，以使不凝气与尾气混合后进入所述尾气吸收塔进行回收利用。
  7. 根据权利要求1-6任一项所述的氨肟化兼回收叔丁醇的反应系统，其特征在于，所述叔丁醇回收塔的类型为垂直筛板塔。
  8. 根据权利要求1-6任一项所述的氨肟化兼回收叔丁醇的反应系统，其特征在于，所述反应系统还包括循环叔丁醇罐，所述循环叔丁醇罐的顶部与所述叔丁醇回流罐的底部连接，所述循环叔丁醇罐的底部与所述肟化反应器的底部连接，以使叔丁醇重新作为反应溶剂利用。
  9. 采用权利要求1-8任一项所述的氨肟化兼回收叔丁醇的反应系统进行肟化反应兼回收叔丁醇的方法，其特征在于，包括如下步骤：
    氨气经过分散破碎成微气泡后，与液相物料进行催化肟化反应；进行所述催化肟化反应过程中，未反应完全的气体进行尾气回收利用，反应产物以清液方式收集后，并对所述反应产物中的叔丁醇进行回收。
  10. 根据权利要求9所述的方法，所述肟化反应的温度为80-82℃，压力为0.18-0.23MPa。
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