WO2021227136A1 - Système de réaction amélioré et procédé de préparation de cyclohexanone par hydrogénation sélective de benzène - Google Patents

Système de réaction amélioré et procédé de préparation de cyclohexanone par hydrogénation sélective de benzène Download PDF

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WO2021227136A1
WO2021227136A1 PCT/CN2020/092789 CN2020092789W WO2021227136A1 WO 2021227136 A1 WO2021227136 A1 WO 2021227136A1 CN 2020092789 W CN2020092789 W CN 2020092789W WO 2021227136 A1 WO2021227136 A1 WO 2021227136A1
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outlet
reactor
benzene
cyclohexanone
micro
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PCT/CN2020/092789
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Chinese (zh)
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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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Priority to DE212020000665.2U priority Critical patent/DE212020000665U1/de
Priority to JP2022600015U priority patent/JP3238259U/ja
Publication of WO2021227136A1 publication Critical patent/WO2021227136A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • 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
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • C07C5/11—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the invention belongs to the technical field of micro-interface strengthening reactions, and in particular relates to a strengthening reaction system and method for preparing cyclohexanone by selective hydrogenation of benzene.
  • Cyclohexanone is a very widely used chemical raw material, which plays an important role in industrial production and daily life. According to its use, cyclohexanone is often divided into two categories: amide and non-amide, 70% of which are Cyclohexanone for amides accounts for most of the amount of cyclohexanone.
  • the commonly used fibers nylon 6 and nylon 66 are prepared from cyclohexanone for amides; because cyclohexanone has high solubility and low volatility, it is also It can be used as an organic solvent, that is, cyclohexanone for non-amides. Cyclohexanone can be mixed with other solvents to adjust the evaporation rate of the system.
  • cyclohexanone also has a wide range of applications in the field of medicine and anti-aging agents. It can be seen from the above that cyclohexanone has become a very important chemical raw material in industrial production, especially in the polyamide industry.
  • the selective hydrogenation of benzene to produce cyclohexanone is currently the latest production process of cyclohexanone, which mainly includes the hydrogenation of benzene to produce cyclohexene.
  • Hydrogen produces cyclohexene.
  • Cyclohexene and acetic acid undergo an esterification reaction under the action of a solid acid catalyst to produce cyclohexyl acetate.
  • the produced cyclohexyl acetate and hydrogen undergo an addition reaction on a ketone catalyst to produce acetic acid and cyclohexanol.
  • Cyclohexanol is dehydrogenated under the action of a dehydrogenation catalyst to obtain cyclohexanone.
  • the process has high conversion rate and selectivity, almost no three wastes are generated, and has high atomic economy.
  • the separation process of cyclohexane/cyclohexene is omitted, which significantly reduces energy consumption.
  • the by-product ethanol can be used in other chemical production, increasing the added value of the product and increasing the benefit.
  • the selective hydrogenation of benzene to produce cyclohexanone has obvious technological advantages, it also has some disadvantages.
  • the gas-liquid mass transfer area of the existing hydrogenation reactor and addition reactor is limited, and the reaction process In this process, the hydrogen and liquid phase materials cannot be fully mixed, the mass transfer efficiency between the gas and the liquid phase is low, the reaction efficiency is low, and the energy consumption is high; on the other hand, the temperature and pressure inside the reactor are high, which leads to the safety of the entire system. And stability is greatly reduced.
  • the first object of the present invention is to provide an enhanced reaction system for the selective hydrogenation of benzene to produce cyclohexanone.
  • the reaction system is equipped with a micro-interface generator at the raw material inlets of the hydrogenation reactor and the addition reactor.
  • the micro-interface generator After the micro-interface generator is set up, on the one hand, hydrogen can be dispersed and broken into micro-sized micro-bubbles, increasing the area of the phase boundary between the hydrogen and the liquid material, so that the mass transfer space is fully satisfied, and the hydrogen in the liquid phase is increased.
  • the residence time in the medium reduces the consumption of hydrogen, thereby greatly improving the reaction efficiency and significantly reducing the energy consumption of the reaction process; on the other hand, it reduces the temperature and pressure inside the reactor, thereby improving the safety and stability of the entire system.
  • the second object of the present invention is to provide a method for preparing cyclohexanone using the above-mentioned intensified reaction system.
  • the method has milder operating conditions, lowers the reaction temperature and pressure while ensuring the reaction efficiency, and has high safety performance and energy efficiency.
  • the consumption is low, and the reaction effect is better than that of the existing process.
  • the present invention provides an enhanced reaction system for the selective hydrogenation of benzene to prepare cyclohexanone, which includes a hydrogenation reactor; the hydrogenation reactor is provided with a discharge port which is connected to a catalyst separator for The catalyst in the reaction product is separated; the top of the catalyst separator is provided with an oil phase outlet, and the oil phase outlet is connected to an esterification reactor for the esterification reaction of cyclohexene and acetic acid;
  • the side wall is provided with a cyclohexyl acetate outlet, the cyclohexyl acetate outlet is connected to an addition reactor for the addition reaction of cyclohexyl acetate and hydrogen; the bottom of the addition reactor is provided with a mixture outlet, so The mixture outlet is connected to an ethanol rectification tower for separating ethanol; the bottom of the ethanol rectification tower is provided with a heavy component outlet, and the heavy component outlet is connected to a cyclohexanol rectifying tower for separating gas phase cyclo
  • the side wall of the hydrogenation reactor is provided with a first raw material inlet, and the first raw material inlet is provided with a first micro-interface generator for dispersing the broken gas into bubbles; the side wall of the addition reactor is provided with The second raw material inlet is provided with a second micro-interface generator for dispersing the crushed gas into bubbles.
  • the reaction of selective hydrogenation of benzene to prepare cyclohexanone has the following problems: On the one hand, the gas-liquid mass transfer area of the existing reactor is limited, and during the reaction process, the reaction mixture raw materials and hydrogen cannot be fully mixed. The energy consumption is large and the reaction efficiency is low; on the other hand, due to the high temperature and pressure during the reaction process, the safety and stability of the entire system cannot be guaranteed.
  • the intensified reaction system for preparing cyclohexanone by the selective hydrogenation of benzene of the present invention can disperse and break hydrogen gas into micrometers in diameter by installing a micro-interface generator at the raw material inlets of the hydrogenation reactor and the addition reactor.
  • the level of microbubbles increases the phase boundary area between the hydrogen and the liquid phase material, so that the mass transfer space is fully satisfied, and the residence time of hydrogen in the liquid phase is increased, reducing the consumption of hydrogen, thereby greatly improving the reaction efficiency, Significantly reduce the energy consumption of the reaction process; on the other hand, reduce the temperature and pressure inside the reactor, thereby improving the safety and stability of the entire system.
  • the bottom of the catalyst separator is provided with a catalyst outlet for recycling the catalyst into the hydrogenation reactor for recycling.
  • the recovered catalyst is returned to the hydrogenation reactor for reuse, reducing the loss of the catalyst, and the catalyst can be continuously taken out, regenerated and replenished, maintaining high activity and high selectivity, so that it can be carried out in a long-term, continuous and stable manner. Production.
  • a kettle liquid outlet is provided at the bottom of the cyclohexanol rectification tower, and the kettle liquid outlet is connected to the esterification reactor for reuse of unreacted cyclohexyl acetate.
  • the reactant contains a small amount of unreacted cyclohexyl acetate, which flows out from the kettle liquid outlet after ethanol distillation and cyclohexanol distillation, and returns to the esterification reactor to participate in the esterification reaction again , Fully improve the utilization rate of raw materials.
  • a hydrogen outlet is provided on the top of the gas-liquid separator, and the hydrogen outlet is connected to the second micro-interface generator for reuse of the separated hydrogen.
  • the product after cyclohexanol dehydrogenation reaction will contain a large amount of hydrogen. This part of hydrogen can be recovered through the gas-liquid separator, which fully improves the utilization rate of hydrogen.
  • the hydrogen outlet is provided with a hydrogen compressor for compressing the hydrogen before recycling.
  • first micro-interface generator and the second micro-interface generator are both pneumatic micro-interface generators; the number of the first micro-interface generator and the second micro-interface generator is at least For more than one.
  • the arrangement of the first micro-interface generator and the second micro-interface generator is not limited, the setting position is not limited, and the number is not limited; more preferably, the number of the micro-interface generator is more than one It is arranged in parallel from top to bottom before the reactor, and the incoming hydrogen can be dispersed and crushed at the same time through the multi-row parallel micro-interface generator, which can effectively improve the subsequent reaction efficiency.
  • micro-interface generator used in the present invention has been embodied in the inventor’s previous patents, such as application numbers CN201610641119.6, 201610641251.7, CN201710766435.0, CN106187660, CN105903425A, CN109437390A, CN205833127U and CN207581700U patents.
  • the prior patent CN201610641119.6 detailed the specific product structure and working principle of the micro-bubble generator (that is, the micro-interface generator).
  • the body is provided with an inlet communicating with the cavity, the opposite first end and the second end of the cavity are both open, and the cross-sectional area of the cavity is from the middle of the cavity to the first end of the cavity and The second end is reduced; the secondary crushing piece is provided at at least one of the first end and the second end of the cavity, a part of the secondary crushing piece is set in the cavity, and the secondary crushing piece is open to both ends of the cavity An annular channel is formed between the through holes.
  • the micro-bubble generator also includes an air inlet pipe and a liquid inlet pipe.” From the specific structure disclosed in the application document, it can be known that the specific working principle is: the liquid enters the micron tangentially through the liquid inlet pipe.
  • the micro-bubble generator In the bubble generator, ultra-high-speed rotation and cutting the gas, the gas bubbles are broken into micron-level micro-bubbles, thereby increasing the mass transfer area between the liquid phase and the gas phase, and the micro-bubble generator in this patent belongs to a pneumatic micro-interface generation Device.
  • the primary bubble breaker has a circulating liquid inlet, a circulating gas inlet and a gas-liquid mixture outlet.
  • the secondary bubble breaker connects the feed port with the gas-liquid mixture outlet, indicating that the bubble breakers are all It needs to be mixed with gas and liquid.
  • the primary bubble breaker mainly uses circulating fluid as power, so in fact, the primary bubble breaker belongs to the hydraulic micro-interface generator, and the secondary bubble breaker is The mixture is simultaneously passed into the elliptical rotating sphere for rotation, so as to achieve bubble breakage during the rotation, so the secondary bubble breaker is actually a gas-liquid linkage micro-interface generator.
  • micro-interface generator used in the present invention is not limited to the above-mentioned forms.
  • the specific structure of the bubble breaker described in the previous patent is only one of the forms that the micro-interface generator of the present invention can adopt.
  • the previous patent 201710766435.0 records that "the principle of the bubble breaker is high-speed jets to achieve gas collisions", and also explained that it can be used in a micro-interface strengthening reactor, verifying the difference between the bubble breaker and the micro-interface generator.
  • the previous patent CN106187660 is also a related record in the previous patent CN106187660 about the specific structure of the bubble breaker. For details, see paragraphs [0031]-[0041] in the specification, as well as the part of the drawings, which is related to the bubble breaker S-2 The specific working principle of the bubble breaker is explained in detail.
  • the top of the bubble breaker is the liquid phase inlet, and the side is the gas phase inlet.
  • the liquid phase coming in from the top provides the entrainment power to achieve the effect of crushing into ultra-fine bubbles, which can also be seen in the attached drawings.
  • the bubble breaker has a cone-shaped structure, and the diameter of the upper part is larger than that of the lower part, which is also for the liquid phase to provide better entrainment power.
  • micro-interface generator Since the micro-interface generator was just developed at the early stage of the patent application, it was named micro-bubble generator (CN201610641119.6) and bubble breaker (201710766435.0) in the early days. With continuous technological improvement, it was later renamed as micro-interface generator. Now the micro-interface generator in the present invention is equivalent to the previous micro-bubble generator, bubble breaker, etc., but the name is different.
  • the micro-interface generator of the present invention belongs to the prior art. Although some bubble breakers are pneumatic bubble breakers, some bubble breakers are hydraulic bubble breakers, and some are pneumatic bubble breakers.
  • the type of liquid-linked bubble breaker but the difference between the types is mainly selected according to the specific working conditions.
  • connection of the micro-interface generator and the reactor, and other equipment, including the connection structure and the connection position, according to the micro-interface It depends on the structure of the interface generator, which is not limited.
  • a benzene refiner for refining raw benzene
  • a refined benzene outlet is provided at the bottom of the benzene refiner
  • the refined benzene outlet is connected to the first micro-interface generator.
  • the benzene refiner is provided with a desulfurization adsorbent packing layer, and the benzene refiner can refine the raw material benzene to remove the sulfur-containing impurities in the raw material benzene.
  • the sulfur content of the benzene from the benzene refiner is less than or equal to 5PPb. , So as to avoid the catalyst poisoning caused by the impurities contained in the raw material benzene.
  • a cyclohexanone reflux tank the bottom of which is provided with a reflux pipeline for returning part of the cyclohexanone to the cyclohexanone rectification tower.
  • a reflux pump is provided on the reflux pipeline.
  • a part of the condensate in the cyclohexanone reflux tank is pressurized by the reflux pump and then returned to the cyclohexanone rectification tower as a reflux pipeline to absorb excess heat at the top of the cyclohexanone rectification tower to maintain
  • the heat balance of the whole tower can also improve the recovery purity of cyclohexanone after multiple refluxing.
  • the reflux pump can be used to adjust the reflux, so that the reflux is stable and the operability is good.
  • the hydrogenation reactor and the addition reactor are both fixed-bed catalytic reactors. Since the internal catalyst of the fixed-bed catalytic reactor is directly loaded on the fixed bed, it is not easy to wear in the bed and can be used for a long time. The structure of the reactor is simple and the operation is convenient.
  • the present invention also provides a method for preparing cyclohexanone by selective hydrogenation of benzene, which includes the following steps:
  • the hydrogen After the hydrogen is dispersed and broken into microbubbles, it undergoes a catalytic hydrogenation reaction with benzene, and an esterification reaction with acetic acid to obtain a reaction product;
  • the crude benzene is first refined by a benzene refiner and then passed into the inside of the first micro-interface generator, and at the same time, hydrogen is passed into the inside of the first micro-interface generator to break it into micro-bubbles with a diameter of micrometers. After being dispersed and broken into microbubbles, it is fully emulsified with benzene.
  • the emulsified liquid enters the hydrogenation reactor for hydrogenation reaction.
  • the reaction product enters the catalyst separator for catalyst separation, and the separated catalyst is returned to the hydrogenation reactor for recycling.
  • the cyclohexene from which the catalyst is removed enters the esterification reactor, and undergoes an esterification reaction with acetic acid under the action of the catalyst, and the esterification product cyclohexyl acetate enters the inside of the second micro-interface generator; at the same time, hydrogen is passed into the second micro-interface
  • the inside of the generator is broken into micro-bubbles with a diameter of micrometers. Hydrogen and cyclohexyl acetate are fully emulsified.
  • the emulsified liquid then enters the addition reactor and undergoes addition reaction under the action of the catalyst.
  • the product enters after ethanol separation.
  • the gas phase cyclohexanol then enters the dehydrogenation reactor for dehydrogenation reaction.
  • the bottom of the cyclohexanol rectification tower contains unreacted cyclohexyl acetate and returns to the addition reactor Reuse, the dehydrogenated product enters the gas-liquid separator to separate hydrogen, and at the same time, the separated hydrogen is returned to the second micro-interface generator for reuse.
  • the alcohol and ketone liquid after the hydrogen is separated finally enters the cyclohexane Cyclohexanone is separated and collected in the ketone distillation tower.
  • the temperature of the hydrogenation reactor is 115-138°C; the pressure is 2.1-2.6 MPa; the temperature of the addition reactor is 185-210°C; the pressure is 2.2-3.1 MPa.
  • the present invention has the following beneficial effects:
  • the intensified reaction system for preparing cyclohexanone by the selective hydrogenation of benzene of the present invention can disperse and break hydrogen gas into micrometers in diameter by installing a micro-interface generator at the raw material inlets of the hydrogenation reactor and the addition reactor.
  • the level of microbubbles increases the phase boundary area between the hydrogen and the liquid phase material, so that the mass transfer space is fully satisfied, and the residence time of hydrogen in the liquid phase is increased, reducing the consumption of hydrogen, thereby greatly improving the reaction efficiency, Significantly reduce the energy consumption of the reaction process; on the other hand, reduce the temperature and pressure inside the reactor, thereby improving the safety and stability of the entire system.
  • Figure 1 is a schematic structural diagram of an enhanced reaction system for selective hydrogenation of benzene to produce cyclohexanone according to an embodiment of the present invention.
  • an enhanced reaction system for the selective hydrogenation of benzene to produce cyclohexanone includes a hydrogenation reactor 10; the hydrogenation reactor 10 is provided with a discharge port 11, The feed port 11 is connected to a catalyst separator 20 for separating the catalyst from the reaction product; the bottom of the catalyst separator 20 is provided with a catalyst outlet 21 for recycling the catalyst into the hydrogenation reactor 10 for recycling, after recovery
  • the catalyst is returned to the hydrogenation reactor 10 for reuse, reducing the loss of the catalyst, and the catalyst can be continuously taken out, regenerated and supplemented, maintaining high activity and high selectivity, so that it can be produced continuously and stably for a long time.
  • An oil phase outlet 22 is provided on the top of the catalyst separator 20, and the oil phase outlet 22 is connected to the esterification reactor 30 for the esterification reaction of cyclohexene and acetic acid; the side wall of the esterification reactor 30 A cyclohexyl acetate outlet 31 is provided, and the cyclohexyl acetate outlet 31 is connected to the addition reactor 40 for the addition reaction of cyclohexyl acetate and hydrogen.
  • the side wall of the hydrogenation reactor 10 is provided with a first raw material inlet 12, and the first raw material inlet 12 is provided with a first micro-interface generator 101 for dispersing crushed gas into bubbles;
  • the side wall of the addition reactor 40 is provided with a second raw material inlet 41, and the second raw material inlet 41 is provided with a second micro-interface generator 401 for dispersing the crushed gas into bubbles.
  • the first micro-interface generator 101 and the second micro-interface generator 401 are both pneumatic micro-interface generators.
  • a mixture outlet 42 is provided at the bottom of the addition reactor 40, and the mixture outlet 42 is connected to an ethanol rectification tower 50 for separating ethanol; the bottom of the ethanol rectification tower 50 is provided with a heavy component outlet 51.
  • the heavy component outlet 51 is connected to the cyclohexanol rectification tower 60, the bottom of the cyclohexanol rectification tower 60 is provided with a kettle liquid outlet 61, and the kettle liquid outlet 61 is connected to the esterification reactor 30 to Used for the reuse of unreacted cyclohexyl acetate; the top of the cyclohexanol rectification tower 60 is provided with a gas phase outlet 62, and the gas phase outlet 62 is connected to the dehydrogenation reactor 70 for the removal of cyclohexanol. Hydrogen reaction.
  • the side wall of the dehydrogenation reactor 70 is provided with a product outlet 71, and the product outlet 71 is connected to a gas-liquid separator 80 for separating hydrogen; the bottom of the gas-liquid separator 80 is provided with alcohol and ketone.
  • the liquid outlet 81, the alcohol and ketone liquid outlet 81 is connected to the cyclohexanone rectification tower 90 for separating cyclohexanone; the top of the gas-liquid separator 80 is provided with a hydrogen outlet 82, and the hydrogen outlet 82 is connected to the
  • the second micro-interface generator 401 is used for the separated hydrogen to be reused.
  • this embodiment also includes a benzene refiner 100 for refining raw benzene.
  • the bottom of the benzene refiner 100 is provided with a refined benzene outlet 110, and the refined benzene outlet 110 is connected to the first micro-interface generator 101. .
  • the cyclohexanone reflux tank 120 is further included, and the bottom of the cyclohexanone reflux tank 120 is provided with a reflux pipeline for returning part of the cyclohexanone to the cyclohexanone rectification tower.
  • the hydrogenation reactor 10 and the addition reactor 40 are both fixed-bed catalytic reactors. Since the internal catalyst of the fixed-bed catalytic reactor is directly loaded on the fixed bed, it is not easy to wear in the bed and can be used for a long time. The structure of the reactor is simple and the operation is convenient.
  • the crude benzene After being refined by the benzene refiner 100, the crude benzene enters the inside of the first micro-interface generator 101. At the same time, hydrogen is passed into the first micro-interface generator 101 to break it into micro-bubbles with a diameter of micrometers. The hydrogen is dispersed and broken into After the microbubbles are fully emulsified with benzene, the emulsified liquid enters the hydrogenation reactor 10 for hydrogenation reaction, the reaction product enters the catalyst separator 20 through the discharge port 11 for catalyst separation, and the separated catalyst is returned through the catalyst outlet 21 again To the inside of the hydrogenation reactor 10 for recycling.
  • the cyclohexene from which the catalyst is removed enters the esterification reactor 30 and undergoes an esterification reaction with acetic acid under the action of the catalyst.
  • the esterification product cyclohexene acetate enters the second micro-interface generator 401 through the cyclohexyl acetate outlet 31, and at the same time
  • the hydrogen is passed into the second micro-interface generator 401 to break it into micro-bubbles with a diameter of micrometers.
  • the hydrogen and cyclohexyl acetate are fully emulsified, and the emulsified liquid then enters the addition reactor 40 and is generated under the action of the catalyst.
  • the product enters the ethanol rectification tower 50 through the mixture outlet 42 to separate ethanol, the separated ethanol mixture then enters the cyclohexanol rectification tower 60, and the gas phase cyclohexanone enters the dehydrogenation reactor 70 through the gas phase outlet 62
  • the dehydrogenation reaction is carried out.
  • the unreacted cyclohexyl acetate is returned to the addition reactor 40 through the kettle liquid outlet 61 for reuse.
  • the dehydrogenated product enters the gas-liquid separator 80 to separate hydrogen, and at the same time, separate
  • the discharged hydrogen is returned to the second micro-interface generator 401 through the hydrogen outlet 82 for reuse, and the alcohol and ketone liquid after the separated hydrogen enters the cyclohexanone rectification tower 90 through the alcohol and ketone liquid outlet 81 for cyclohexanone rectification. Separation and collection.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un système de réaction amélioré et un procédé de préparation de cyclohexanone par hydrogénation sélective de benzène. Le système comprend un réacteur d'hydrogénation (10) ; le réacteur d'hydrogénation (10) est pourvu d'un orifice d'évacuation (11), et l'orifice d'évacuation (11) est relié à un séparateur de catalyseur (20) pour séparer un catalyseur dans un produit de réaction ; le fond d'un séparateur gaz-liquide (80) est pourvu d'une sortie de cétone alcoolique liquide (81), et la sortie de cétone alcoolique liquide (81) est reliée à une tour de rectification de cyclohexanone (90) pour séparer la cyclohexanone ; la paroi latérale du réacteur d'hydrogénation (10) est pourvue d'une première entrée de matière première (12), et la première entrée de matière première (12) est pourvue d'un premier générateur de micro-interface (101) pour disperser et dissocier un gaz en bulles ; la paroi latérale d'un réacteur d'addition (40) est pourvue d'une deuxième entrée de matière première (41), et la deuxième entrée de matière première (41) est pourvue d'un deuxième générateur de micro-interface (401) pour disperser et dissocier un gaz en bulles. Une fois que les générateurs de micro-interface sont disposés au niveau des entrées de matière première du réacteur d'hydrogénation (10) et du réacteur d'addition (40), l'aire de transfert de masse entre l'hydrogène et un matériau en phase liquide est augmentée, et l'efficacité de réaction est améliorée ; de plus, la température et la pression de réaction sont réduites, et la sécurité et la stabilité de l'ensemble du système sont améliorées.
PCT/CN2020/092789 2020-05-14 2020-05-28 Système de réaction amélioré et procédé de préparation de cyclohexanone par hydrogénation sélective de benzène WO2021227136A1 (fr)

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DE212020000665.2U DE212020000665U1 (de) 2020-05-14 2020-05-28 Verstärktes Reaktionssystem zum Herstellen vom Cyclohexanon durch selektive Hydrierung vom Benzol
JP2022600015U JP3238259U (ja) 2020-05-14 2020-05-28 ベンゼンを選択的に水素化してシクロヘキサノンを製造する強化反応システム

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CN114471377B (zh) * 2020-10-28 2023-07-04 中国石油化工股份有限公司 一种重整生成油脱烯烃反应器及反应方法

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