WO2023015706A1 - 一种催化氧化装置和方法 - Google Patents

一种催化氧化装置和方法 Download PDF

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WO2023015706A1
WO2023015706A1 PCT/CN2021/122793 CN2021122793W WO2023015706A1 WO 2023015706 A1 WO2023015706 A1 WO 2023015706A1 CN 2021122793 W CN2021122793 W CN 2021122793W WO 2023015706 A1 WO2023015706 A1 WO 2023015706A1
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reaction
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liquid
catalytic oxidation
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于吉红
唐康健
陈少昂
康振辉
王肖
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Suzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B33/00—Oxidation in general
    • 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
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • 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
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to a catalytic reaction, in particular to a catalytic oxidation device and method.
  • adipic acid there are two main production processes for adipic acid: (1) Cyclohexane method, catalytic hydrogenation of pure benzene to generate cyclohexane, and oxidation to cyclohexane under the conditions of O 2 , 0.8-1.5MPa, 125-165°C
  • the mixed intermediate product (KA oil) of hexanone and cyclohexanol and then use 50%-65% HNO3 to oxidize KA oil at 60-80°C to generate adipic acid
  • (2) cyclohexene method pure benzene Carry out partial hydrogenation to generate cyclohexene, hydration reaction at 0.5MPa and 120°C to generate cyclohexanol, and then use HNO3 to oxidize cyclohexanol to generate adipic acid.
  • the production process is lengthy, high energy consumption, corroded equipment, and serious environmental pollution.
  • the synthesis methods of 1-adamantanol mainly fall into four categories: bromide hydrolysis, direct oxidation, adamantane sulfonate hydrolysis, and adamantane nitrate hydrolysis.
  • Patent CN101492348A reports that bromine is used as a halogenating agent to brominate adamantane and hydrolyze it to obtain 1-adamantanol. This method uses a large amount of bromine, which is expensive and inconvenient to transport.
  • Patent EP084428A reports the use of NHPI and cobalt ions to catalyze the direct reaction of adamantane with oxygen to generate 1-adamantanol.
  • Patent CN101891570A reports the use of oleum and acetonitrile to sulfonate adamantane and hydrolyze it to obtain 1-adamantanol. This method uses a large amount of oleum, resulting in a large amount of strongly acidic wastewater, which is extremely difficult to treat and causes environmental pollution.
  • Patent CN102276375 reports the use of nitric acid to react with adamantane to form nitrate ester, which is hydrolyzed to obtain 1-adamantanol. This method has poor selectivity, and the use of nitric acid causes a large amount of NOx emissions, which seriously pollutes the environment.
  • the present invention aims to solve the above problems, and provides a catalytic oxidation device and method, which have the advantages of high efficiency, energy saving, no equipment corrosion, environmental friendliness, and high-quality products.
  • the catalytic oxidation device includes a sequentially connected storage unit, a premixing unit, a microchannel reaction unit, a gas-liquid separation unit, a solid-liquid separation unit, and a product purification unit;
  • the storage unit is used for independent Store oxygen-containing gas, raw materials and catalyst dispersion liquid, the raw materials are mono-substituted or double-substituted benzene, C4-C6 alkane or C6-C12 cycloalkane, the substituent of mono-substituted or double-substituted benzene is C1-C4 alkane ;
  • the product purification unit is also connected to the premix unit through a circulation pipeline.
  • the premixing unit is used for the premixing of raw materials (oxygen-containing gas, raw materials and catalyst dispersion)
  • the microchannel reaction unit is used for the catalytic reaction of the premixed raw materials
  • the gas-liquid separation unit is used for the catalytic reaction of the raw materials after the catalytic reaction.
  • Liquid separation, solid-liquid separation unit is used for the crystallization of the liquid obtained from gas-liquid separation.
  • the reacted solution rich in catalyst dispersion is circulated, which greatly improves the utilization rate of raw materials and catalysts and product yield, and reduces production costs.
  • gas outlet of the gas-liquid separation unit is provided with a tail gas treatment unit for processing the gas obtained from gas-liquid separation.
  • the premixing unit is selected from one or more of a gas-liquid mixer, a static mixer, a high-shear mixing pump, and a premixer.
  • microchannel reaction unit is selected from at least one of intercalation microchannel reactors, star microchannel reactors, plate microchannel reactors, microbubble reactors or gas-liquid enhanced reactors.
  • the gas-liquid separation unit is selected from one or more of separators such as static gas-liquid separators, centrifugal gas-liquid separators, and gas-liquid separation tanks.
  • the solid-liquid separation unit is selected from one or more of crystallizers, self-cooling tanks, solid-liquid separators, plate and frame filter presses, and the like.
  • the product purification unit is selected from one or more of purification equipment such as a condenser, a suspension separator, an evaporation tank, a crystallizer, a plate and frame filter, and a reboiler.
  • purification equipment such as a condenser, a suspension separator, an evaporation tank, a crystallizer, a plate and frame filter, and a reboiler.
  • the catalyst dispersion is a carbon-based material dispersion
  • the carbon-based material is selected from carbon quantum dots, hydroxyl-modified carbon quantum dots, carboxyl-modified carbon quantum dots, carbonyl-modified carbon quantum dots, graphene, One or more of carbon nanotubes, metal-loaded carbon quantum dots, and heteroatom-doped carbon quantum dots.
  • the solvent in the catalyst dispersion is methanol, ethanol, propanol, butanol, acetone, butanone, methylene chloride, chloroform, chloroform, ethyl acetate, ether, petroleum ether, toluene, xylene , one or more of dimethylformamide, dimethyl sulfoxide and water.
  • the raw material is cyclohexane, n-hexane, adamantane or decahydronaphthalene.
  • Another aspect of the present invention provides a catalytic oxidation method, using the above catalytic oxidation device, comprising the following steps,
  • S1 Transport the oxygen-containing gas, raw materials and catalyst dispersion stored in the storage unit to the premixing unit for premixing;
  • the catalytic oxidation device includes a storage unit, a premixing unit, a microchannel reaction unit, a gas-liquid separation unit, a solid-liquid separation unit and a product purification unit connected in sequence; the product purification unit is also connected to the premixing unit through a circulation pipeline. unit.
  • the product when the raw material is cyclohexane, the product is adipic acid; when the raw material is n-hexane, the product is 2,5-hexanedione; when the raw material is toluene, the product is benzaldehyde and benzoic acid; when the raw material is ethylbenzene , the product is acetophenone; when the raw material is adamantane, the product is 1-adamantanol; when the raw material is decalin, the product is 9-decalinol.
  • step S3 the gas separated in step S3 is treated by the tail gas treatment unit and then evacuated, and the crystallization in step S4 is low-temperature (0-8° C.) crystallization.
  • the pressure in the premixing unit and the microchannel reaction unit is 0.1-10 MPa.
  • the pressure in the premix unit and the microchannel reaction unit is 0.1-10MPa, preferably 3MPa; when the raw material is n-hexane or adamantane, the pressure in the premix unit and the microchannel reaction unit 0.1-5MPa, preferably 1.5MPa.
  • the temperature in the microchannel reaction unit is 4-300°C.
  • the temperature in the microchannel reaction unit is 4-300°C, preferably 150°C; when the raw material is n-hexane or adamantane, the temperature in the microchannel reaction unit is 20-200°C, Preferably it is 140°C.
  • the reaction time is 0.01-240min.
  • the reaction time is 0.01-240 min, preferably 15 min; when the raw material is n-hexane or adamantane, the reaction time is 0.1-200 min, preferably 30 min.
  • the oxygen content in the oxygen-containing gas is 0.1%-100%.
  • air with an oxygen content of 21%) is preferred; when the raw material is n-hexane or adamantane, pure oxygen is preferred.
  • the concentration of the catalyst dispersion is 0.8-2.0 g/L.
  • the rate ratio of the raw material and the catalyst dispersion liquid entering the microchannel reaction unit is 1:2-5.
  • the beneficial effect of the present invention is that: the method of using oxygen for oxidation and gas-liquid phase catalytic reaction in the microchannel reaction unit fully mixes alkanes with oxygen, catalyzes and generates oxidation products, does not need nitric acid as an oxidant, greatly reduces production costs, and is effective The problem of environmental pollution is greatly avoided; the high-efficiency mass transfer characteristics of the microchannel reactor are used to greatly improve the reaction efficiency; after the product is separated, the residual reaction liquid and the catalyst dispersion liquid are co-circulated to realize the full utilization of raw materials and catalysts.
  • Fig. 1 is a structural schematic diagram of the present invention.
  • 1-air storage tank 2-raw material storage tank
  • 3-catalyst dispersion liquid storage tank 4-first advection pump, 5-second advection pump, 6-second crystallizer, 7-first Crystallizer, 8-gas-liquid separation tank, 9-tail gas processor, 10-microchannel reactor, 11-gas-liquid premixer, 12-third advection pump.
  • a catalytic oxidation device including a storage unit, a premixing unit, a microchannel reaction unit, a gas-liquid separation unit, a solid-liquid separation unit and a product purification unit connected in sequence; the storage unit is used to store oxygen-containing gas, raw materials and catalyst dispersion respectively liquid, the product purification unit is also connected to the premixing unit through a circulation pipeline.
  • storage unit comprises three raw material tanks, is respectively air storage tank 1, raw material storage tank 2 and catalyst dispersion liquid storage tank 3, and premixing unit adopts gas-liquid premixer 11;
  • the pipeline between the tank 2 and the gas-liquid premixer 11 is provided with the first advection pump, and the pipeline between the catalyst dispersion storage tank 3 and the gas-liquid premixer 11 is provided with the first advection pump 5;
  • the microchannel reaction The unit adopts a microchannel reactor 10, the gas-liquid separation unit adopts a gas-liquid separation tank 8, and the gas outlet of the gas-liquid separation tank 8 is connected to the tail gas processor 9;
  • the solid-liquid separation unit adopts the first crystallizer 7, and the first crystallizer 7 passes through
  • the circulation pipeline is connected to the gas-liquid premixer 11, and the third advection pump 12 is arranged on the circulation pipeline;
  • the product purification unit adopts the second crystallizer 6.
  • the reaction After the reaction, it enters the gas-liquid separation tank 8, and the gas part is mainly oxygen-poor air, which is emptied after treatment.
  • the liquid enters the first crystallizer 7 for tertiary crystallization (the temperature of each crystallization tank is 5° C.).
  • the remaining reaction liquid is transported to the gas-liquid pre-mixer 11 by the third advection pump 12 for circulation.
  • the crystallized product is crude adipic acid.
  • the crude product enters the second crystallizer 6 for three times of recrystallization to obtain high-quality adipic acid. According to liquid chromatography analysis, the selectivity of adipic acid is 97.6%, and the one-pass conversion rate of cyclohexane is 40.37%.
  • Oxygen-containing gas (composed of 10% oxygen and 90% nitrogen) enters the reaction system through the micropores of the reactor, the gas flow rate is controlled to 500mL/min, and the internal pressure of the reaction system is 1MPa, followed by oxidation reaction (the microchannel material is Hastelloy , the residence time is 15min). After the reaction, it enters the gas-liquid separation tank. The gas part is mainly oxygen-poor and non-toxic gas, which is emptied after treatment. The liquid enters the crystallizer for tertiary crystallization (the temperature of each crystallization tank is 5°C). After solid-liquid separation, the remaining reaction liquid is transported to the pre-mixer by the advection pump for circulation. The crystallized product was crude adipic acid.
  • the crude product was recrystallized three times to obtain high-quality adipic acid.
  • the selectivity of adipic acid was 79.75% according to liquid chromatography analysis, and the one-pass conversion rate of cyclohexane was 7.42%.
  • the reaction After the reaction, it enters the gas-liquid separation tank.
  • the gas part is mainly oxygen-poor and non-toxic gas, which is emptied after treatment.
  • the liquid enters the crystallizer for tertiary crystallization (the temperature of each crystallization tank is 5°C).
  • the remaining reaction liquid After solid-liquid separation, the remaining reaction liquid is transported to the pre-mixer by the advection pump for circulation.
  • the crystallized product is crude adipic acid.
  • the crude product was recrystallized three times to obtain high-quality adipic acid.
  • the selectivity of adipic acid was 90.32% according to liquid chromatography analysis, and the one-pass conversion rate of cyclohexane was 8.66%.
  • the reaction After the reaction, it enters the gas-liquid separation tank.
  • the gas part is mainly oxygen-poor and non-toxic gas, which is emptied after treatment.
  • the liquid enters the crystallizer for tertiary crystallization (the temperature of each crystallization tank is 5°C).
  • the remaining reaction liquid After solid-liquid separation, the remaining reaction liquid is transported to the pre-mixer by the advection pump for circulation.
  • the crystallized product is crude adipic acid.
  • the crude product was recrystallized three times to obtain high-quality adipic acid.
  • the selectivity of adipic acid was 92.35% according to liquid chromatography analysis, and the one-pass conversion rate of cyclohexane was 70.51%.
  • the carbon quantum dots were replaced by hydroxyl-modified carbon quantum dots, carboxyl-modified carbon quantum dots, carbonyl-modified carbon quantum dots, graphene, carbon nanotubes, metal-loaded carbon quantum dots, heteroatoms Doped carbon quantum dots, a mixture of carbon quantum dots and carboxyl-modified carbon quantum dots.
  • acetone is replaced by methanol, ethanol, propanol, butanol, butanone, dichloromethane, chloroform, chloroform, ethyl acetate, ether, petroleum ether, toluene, xylene, di Aqueous solutions of methylformamide, dimethyl sulfoxide, water, methanol.
  • gas-liquid separation is carried out, and the gas part is mainly oxygen-depleted air, which is emptied after treatment.
  • the liquid is distilled under reduced pressure, dried, and rectified to obtain a colorless liquid product, 2,5-hexanedione, and the remaining reaction liquid is sent to a premixing device for circulation.
  • the purity of 2,5-hexanedione was 94.9%, and the one-way conversion rate of n-hexane was 25.6%.
  • Premix with the reaction system control the oxygen flow rate to 300mL/min, and the internal pressure of the reaction system to 1.5MPa, and then enter the constant temperature microchannel reactor at 150°C for catalytic oxidation reaction, the residence time is 20min.
  • gas-liquid separation is carried out, and the gas part is mainly low-concentration oxygen, which is emptied after treatment.
  • the liquid is crystallized, filtered, dried, and recrystallized to obtain a white crystalline solid product 1-adamantanol, and the remaining reaction liquid is sent to a premixing device for circulation.
  • the purity of 1-adamantanol was 98.4% through chromatographic analysis, and the one-pass conversion rate of adamantane was 62.5%.
  • Premix with the reaction system control the air flow rate to 500mL/min, and the internal pressure of the reaction system to 1.5MPa, and then enter the constant temperature microchannel reactor at 150°C for catalytic oxidation reaction, the residence time is 20min.
  • gas-liquid separation is carried out, and the gas part is mainly oxygen-depleted air, which is emptied after treatment.
  • the liquid is crystallized, filtered, dried, and recrystallized to obtain a white crystalline solid product 1-adamantanol, and the remaining reaction liquid is sent to a premixing device for circulation.
  • the purity of 1-adamantanol was 98.9% through chromatographic analysis, and the one-pass conversion rate of adamantane was 30.6%.
  • the reaction gas-liquid separation is carried out, and the gas part is mainly low-concentration oxygen, which is emptied after treatment.
  • the crude product of benzoic acid is obtained by liquid crystallization, and benzoic acid is obtained by recrystallization; the remaining liquid is distilled under normal pressure, dried, and rectified to obtain benzaldehyde, a colorless oily liquid product, and the remaining reaction liquid is transported to a premixing device for circulation.
  • the purity of benzoic acid is 97.1%
  • the purity of benzaldehyde is 98.5%
  • the one-way conversion rate of toluene is 22.7%.
  • the carbon quantum dot catalysts in the above-mentioned Examples 1-28, 37-59 are prepared from powdered graphite after multiple times of UV irradiation and grinding.

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Abstract

本发明涉及一种催化反应，具体涉及一种催化氧化装置和方法，所述催化氧化装置，包括依次连通的存储单元、预混单元、微通道反应单元、气液分离单元、固液分离单元和产物纯化单元；所述产物纯化单元还通过循环管道连接至所述预混单元。本发明使用氧气进行氧化、气液相在微通道反应单元进行催化反应的方法将烷烃与氧气充分混合，催化生成氧化产物，不需要硝酸作为氧化剂，大大降低了生产成本，有效地避免了环境污染问题；利用微通道反应器的高效传质特点，极大提高反应效率；产物分离后将反应余液液体及催化剂分散液进行共循环，实现了原料与催化剂等的充分利用。

Description

一种催化氧化装置和方法 技术领域
本发明涉及一种催化反应，具体涉及一种催化氧化装置和方法。
背景技术
现有技术中，烷烃氧化产物的制备工艺要么流程冗长、复杂，能耗巨大，要么氧化环节所使用的硝酸等强酸造成设备腐蚀并产生大量NO x废气、废液。
如己二酸的生产工艺主要为两种：(1)环己烷法，对纯苯进行催化加氢生成环己烷，在O 2、0.8-1.5MPa、125-165℃条件下氧化生成环己酮及环己醇混合中间产物(KA油)，后在60-80℃条件下使用50％-65％HNO 3对KA油氧化生成己二酸；(2)环己烯法，对纯苯进行部分加氢生成环己烯，在0.5MPa、120℃条件下水合反应生成环己醇，后使用HNO 3对环己醇氧化生成己二酸。所述生产工艺冗长、能耗高、腐蚀设备、环境污染严重。
2,5-己二酮的合成方法主要为两种：(1)2,5-二甲基呋喃水解法，该法虽操作简单反应条件温和，但副反应多，产物分离困难。(2)乙酰乙酸乙酯钠与纯碘反应生成二乙酰琥珀酸二乙酯；再将其与10％氢氧化钠溶液进行水解，用无水碳酸钾使反应液饱和，析出丙酮基丙酮，用乙醚提取，从提取液蒸去乙醚后，蒸馏剩余物，收集192-194℃馏分得无色产品；该法流程冗长，成本高，且环境污染严重，极大限制了相关技术在产业化方面的应用。
1-金刚烷醇的合成方法主要为四类：溴代物水解法、直接氧化法、金刚烷磺化物水解法、金刚烷硝酸酯水解法。专利CN101492348A中报道以溴素作为卤化剂，对金刚烷进行溴化，经水解得到1-金刚烷醇。该法使用大量溴素，价格昂贵且运输不便。专利EP084428A中报道利用NHPI和钴离子催化金刚烷与氧气直接反应生成1-金刚烷醇。该法选择性差，副产多，产品分离工艺复杂，且催化剂中的有毒金属对环境污染严重。专利CN101891570A中报道使用发烟硫 酸及乙腈对金刚烷进行磺化，经水解得到1-金刚烷醇。该法使用大量发烟硫酸，造成大量强酸性废水，处理极其困难，造成环境污染。专利CN102276375中报道使用硝酸与金刚烷反应生成硝酸酯，经水解得到1-金刚烷醇，该法选择性差，硝酸的使用造成大量NO x排放，对环境污染严重。
综上，烷烃氧化产物的制备中存在的问题，大大地限制了其生产工艺效率与效益。
发明内容
本发明旨在解决上述问题，提供了一种催化氧化装置和方法，具有高效节能、无设备腐蚀、环境友好、产物高品质的优点。
按照本发明的技术方案，所述催化氧化装置，包括依次连通的存储单元、预混单元、微通道反应单元、气液分离单元、固液分离单元和产物纯化单元；所述存储单元用于独立存储含氧气体、原料和催化剂分散液，所述原料为单取代或双取代的苯、C4-C6链烷烃或C6-C12环烷烃，单取代或双取代的苯的取代基为C1-C4烷烃；所述产物纯化单元还通过循环管道连接至所述预混单元。
具体的，预混单元用于原料(含氧气体、原料和催化剂分散液)的预混，微通道反应单元用于预混后原料的催化反应，气液分离单元用于催化反应后原料的气液分离，固液分离单元用于气液分离所得液体的结晶。
本发明将反应后的富含催化剂分散液的溶液进行循环操作，极大地提高了原料、催化剂的利用率及产物产率，降低了生产成本。
进一步的，所述气液分离单元的出气口设有尾气处理单元，用于气液分离所得气体的处理。
进一步的，预混单元选自气液混合器、静态混合器、高剪切混合泵、预混器中的一种或多种。
进一步的，微通道反应单元选自插层微通道反应器、星型微通道反应器、板式微通道反应器、微气泡反应器或气液强化反应器等反应器中的至少一种。
进一步的，气液分离单元选自静态气液分离器、离心式气液分离器、气液 分离罐等分离器中的一种或多种。
进一步的，固液分离单元选自结晶器、自降温槽、固液分离机、板框式压滤机等中的一种或多种。
进一步的，产物纯化单元选自冷凝器、悬液分离器、蒸发罐、结晶器、板框过滤机及再沸器等纯化设备中的一种或多种。
进一步的，所述催化剂分散液为碳基材料分散液，所述碳基材料选自碳量子点、羟基改性碳量子点、羧基改性碳量子点、羰基改性碳量子点、石墨烯、碳纳米管、金属负载碳量子点和杂原子掺杂碳量子点中的一种或多种。
进一步的，所述催化剂分散液中的溶剂为甲醇、乙醇、丙醇、丁醇、丙酮、丁酮、二氯甲烷、三氯甲烷、氯仿、乙酸乙酯、乙醚、石油醚、甲苯、二甲苯、二甲基甲酰胺、二甲基亚砜和水中的一种或多种。
优选的，所述原料为环己烷、正己烷、金刚烷或十氢萘。
本发明的另一方面提供了一种催化氧化方法，采用上述催化氧化装置，包括以下步骤，
S1：将存储单元存储的含氧气体、原料和催化剂分散液输送至预混单元进行预混；
S2：经预混的含氧气体、原料和催化剂分散液进入微通道反应单元进行反应；
S3：反应后所得气液混合物输送至气液分离单元进行分离；
S4：分离所得的液体进入固液分离单元进行结晶，得到产物晶体；
S5：所得产物晶体进入产物纯化单元提纯得到产物；固液分离单元内含催化剂的溶液沿循环管道返回预混单元进入生产循环。
所述催化氧化装置包括依次连通的存储单元、预混单元、微通道反应单元、气液分离单元、固液分离单元和产物纯化单元；所述产物纯化单元还通过循环管道连接至所述预混单元。
具体的，原料为环己烷时，产物为己二酸；原料为正己烷时，产物为2,5- 己二酮；原料为甲苯时，产物为苯甲醛及苯甲酸；原料为乙苯时，产物为苯乙酮；原料为金刚烷时，产物为1-金刚烷醇；原料为十氢萘时，产物为9-十氢萘醇。
进一步的，步骤S3分离所得气体经尾气处理单元处理后排空，步骤S4中结晶为低温(0-8℃)结晶。
进一步的，所述预混单元和微通道反应单元内的压强为0.1-10MPa。
具体的，原料为环己烷时，预混单元及微通道反应单元内的压强为0.1-10MPa，优选为3MPa；原料为正己烷或金刚烷时，预混单元及微通道反应单元内的压强为0.1-5MPa，优选为1.5MPa。
进一步的，微通道反应单元内的温度为4-300℃。
具体的，原料为环己烷时，微通道反应单元内的温度为4-300℃，优选为150℃；原料为正己烷或金刚烷时，微通道反应单元内的温度为20-200℃，优选为140℃。
进一步的，所述步骤S2中，反应的时间为0.01-240min。
具体的，原料为环己烷时，反应的时间为0.01-240min，优选为15min；原料为正己烷或金刚烷时，反应的时间为0.1-200min，优选30min。
进一步的，以体积占比计，所述含氧气体中的含氧量为0.1％-100％。具体的，原料为环己烷时，优选空气(含氧量21％)；原料为正己烷或金刚烷时，优选为纯氧。
进一步的，催化剂分散液的浓度为0.8-2.0g/L。
进一步的，原料和催化剂分散液进入微通道反应单元的速率比为1：2-5。
本发明的有益效果在于：使用氧气进行氧化、气液相在微通道反应单元进行催化反应的方法将烷烃与氧气充分混合，催化生成氧化产物，不需要硝酸作为氧化剂，大大降低了生产成本，有效地避免了环境污染问题；利用微通道反应器的高效传质特点，极大提高反应效率；产物分离后将反应余液及催化剂分散液进行共循环，实现了原料与催化剂等的充分利用。
附图说明
图1为本发明的结构示意图。
附图标记说明：1-空气储罐、2-原料储罐、3-催化剂分散液储罐、4-第一平流泵、5-第二平流泵、6-第二结晶器、7-第一结晶器、8-气液分离罐、9-尾气处理器、10-微通道反应器、11-气液预混器、12-第三平流泵。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
一种催化氧化装置，包括依次连接的存储单元、预混单元、微通道反应单元、气液分离单元、固液分离单元和产物纯化单元；存储单元用于分别存储含氧气体、原料和催化剂分散液，产物纯化单元还通过循环管道连接预混单元。
如图1所示的实施例中，存储单元包括三个原料罐，分别为空气储罐1、原料储罐2和催化剂分散液储罐3，预混单元采用气液预混器11；原料储罐2与气液预混器11之间的管道上设有第一平流泵，催化剂分散液储罐3与气液预混器11之间的管道上设有第一平流泵5；微通道反应单元采用微通道反应器10，气液分离单元采用气液分离罐8，气液分离罐8的出气口连接尾气处理器9；固液分离单元采用第一结晶器7，第一结晶器7通过循环管道连接气液预混器11，循环管道上设有第三平流泵12；产物纯化单元采用第二结晶器6。
实施例1
采用图1所示装置。称取5g碳量子点催化剂于5L丙酮中，超声分散10min后储存在原料罐中，另一原料罐中为环己烷。环己烷以5mL/min的速率输送至气液预混器11，碳量子点的丙酮分散液以15mL/min的速率输送至气液预混器11，空气在气液预混器中与反应体系进行预混，控制空气流速为500mL/min，反应体系内压为3MPa，后进入150℃的恒温微通道反应器10进行催化氧化反应(微通道材质为哈氏合金，停留时间为15min)。反应后进入气液分离罐8，气体部分主要为贫氧空气，经处理后排空。液体进入第一结晶器7进行三级结晶 (各结晶槽温度均为5℃)，经固液分离后，反应余液经第三平流泵12输送至气液预混器11进行循环。结晶产物为粗己二酸，粗品进入第二结晶器6进行三次重结晶得到高品质己二酸，经液相色谱分析己二酸选择性为97.6％，环己烷单程转化率为40.37％。
实施例2
称取5g碳量子点催化剂于5L丙酮中，超声分散10min后储存在原料罐中，另一原料罐中为环己烷。环己烷以5mL/min的速率输送至气液预混器，碳量子点的丙酮分散液以15mL/min的速率输送至气液预混器，后进入130℃的恒温板式微气泡反应器，含氧气体(由10％氧气和90％氮气组成)通过反应器微孔进入反应体系，控制气体流速为500mL/min，反应体系内压为1MPa，随后进行氧化反应(微通道材质为哈氏合金，停留时间为15min)。反应后进入气液分离罐，气体部分主要为贫氧无毒害气体，经处理后排空。液体进入结晶器进行三级结晶(各结晶槽温度均为5℃)，经固液分离后，反应余液经平流泵输送至预混器进行循环。结晶产物为粗己二酸，将粗品进行三次重结晶得到高品质己二酸，经液相色谱分析己二酸选择性为79.75％，环己烷单程转化率为7.42％。
实施例3
称取5g碳量子点催化剂于5L丙酮中，超声分散10min后储存在原料罐中，另一原料罐中为环己烷。环己烷以5mL/min的速率输送至预混器，碳量子点的丙酮分散液以15mL/min的速率输送至预混器，后进入100℃的恒温板式微气泡反应器，空气(由21％氧气和79％氮气组成)通过反应器微孔进入反应体系，控制空气流速为500mL/min，反应体系内压为3MPa，随后进行氧化反应(微通道材质为哈氏合金，停留时间为15min)。反应后进入气液分离罐，气体部分主要为贫氧无毒害气体，经处理后排空。液体进入结晶器进行三级结晶(各结晶槽温度均为5℃)，经固液分离后，反应余液经平流泵输送至预混器进行循环。结晶产物为粗己二酸，将粗品进行三次重结晶得到高品质己二酸，经液相色谱分析己二酸选择性为90.32％，环己烷单程转化率为8.66％。
实施例4
称取5g碳量子点催化剂于5L丙酮中，超声分散10min后储存在原料罐中，另一原料罐中为环己烷。环己烷以5mL/min的速率输送至预混器，碳量子点的丙酮分散液以15mL/min的速率输送至预混器，后进入130℃的恒温板式微气泡反应器，高纯氧气通过反应器微孔进入反应体系，控制气体流速为500mL/min，反应体系内压为3MPa，随后进行氧化反应(微通道材质为哈氏合金，停留时间为15min)。反应后进入气液分离罐，气体部分主要为贫氧无毒害气体，经处理后排空。液体进入结晶器进行三级结晶(各结晶槽温度均为5℃)，经固液分离后，反应余液经平流泵输送至预混器进行循环。结晶产物为粗己二酸，将粗品进行三次重结晶得到高品质己二酸，经液相色谱分析己二酸选择性为92.35％，环己烷单程转化率为70.51％。
实施例5-11
按照实施例2的方法，只是改变反应温度，压力，停留时间，得到不同环己烷单程转化率及己二酸选择性。
实施例12-24
按照实施例3的方法，只是改变反应温度，压力，停留时间，得到不同环己烷单程转化率及己二酸选择性。
实施例25-28
按照实施例4的方法，只是改变反应温度，压力，停留时间，得到不同环己烷单程转化率及己二酸选择性。
具体实施例条件和结果见下表：
Figure PCTCN2021122793-appb-000001
Figure PCTCN2021122793-appb-000002
实施例29-36
按照实施例1的方法，将碳量子点分别替换为羟基改性碳量子点、羧基改性碳量子点、羰基改性碳量子点、石墨烯、碳纳米管、金属负载碳量子点、杂原子掺杂碳量子点、碳量子点和羧基改性碳量子点的混合物。
实施例37-53
按照实施例1的方法，将丙酮分别替换为甲醇、乙醇、丙醇、丁醇、丁酮、二氯甲烷、三氯甲烷、氯仿、乙酸乙酯、乙醚、石油醚、甲苯、二甲苯、二甲基甲酰胺、二甲基亚砜、水、甲醇的水溶液。
实施例54
称取10g碳量子点催化剂于5L丙酮中，超声分散10min后备用。正己烷以3mL/min的速率输送至气液预混器，碳量子点的丙酮分散液以9mL/min的速率输送至气液预混器，氧气在气液预混器中与反应体系进行预混，控制氧气流速为250mL/min，反应体系内压为1.5MPa，后进入140℃的恒温微通道反应器进行催化氧化反应，停留时间为30min。反应后进行气液分离，气体部分主要为低浓度氧气，经处理后排空。液体经减压蒸馏、干燥、精馏得到无色液体产品2,5-己二酮，反应余液输送至预混装置进行循环。经色谱分析2,5-己二酮纯度为96.2％，正己烷单程转化率为37.2％。
实施例55
称取10g碳量子点催化剂于5L丙酮中，超声分散10min备用。正己烷以2mL/min的速率输送至气液预混器，碳量子点的丙酮分散液以6mL/min的速率输送至气液预混器，空气在气液预混器中与反应体系进行预混，控制空气流速为500mL/min，反应体系内压为1.5MPa，后进入140℃的恒温微通道反应器进行催化氧化反应，停留时间为45min。反应后进行气液分离，气体部分主要为贫氧空气，经处理后排空。液体经减压蒸馏、干燥、精馏得到无色色液体产品2,5-己二酮，反应余液输送至预混装置进行循环。经色谱分析2,5-己二酮纯度为94.9％，正己烷单程转化率为25.6％。
实施例56
称取10g碳量子点催化剂于5L丙酮中，超声分散10min后备用，称取50g金刚烷于5L丙酮中，超声分散10min后备用。金刚烷的丙酮溶液以5mL/min的速率输送至气液预混器，羟基改性碳量子点的丙酮分散液以15mL/min的速率输送至气液预混器，氧气在气液预混器中与反应体系进行预混，控制氧气流速为300mL/min，反应体系内压为1.5MPa，后进入150℃的恒温微通道反应器进行催化氧化反应，停留时间为20min。反应后进行气液分离，气体部分主要为低浓度氧气，经处理后排空。液体经结晶、过滤、干燥、重结晶得到白色结晶性固体产品1-金刚烷醇，反应余液输送至预混装置进行循环。经色谱分析1-金刚 烷醇纯度为98.4％，金刚烷单程转化率为62.5％。
实施例57
称取10g碳量子点催化剂于5L丙酮中，超声分散10min后备用，称取50g金刚烷于5L丙酮中，超声分散10min后备用。金刚烷的丙酮溶液以5mL/min的速率输送至气液预混器，羟基改性碳量子点的丙酮分散液以15mL/min的速率输送至气液预混器，氧气在气液预混器中与反应体系进行预混，控制空气流速为500mL/min，反应体系内压为1.5MPa，后进入150℃的恒温微通道反应器进行催化氧化反应，停留时间为20min。反应后进行气液分离，气体部分主要为贫氧空气，经处理后排空。液体经结晶、过滤、干燥、重结晶得到白色结晶性固体产品1-金刚烷醇，反应余液输送至预混装置进行循环。经色谱分析1-金刚烷醇纯度为98.9％，金刚烷单程转化率为30.6％。
实施例58
称取10g碳量子点催化剂于5L丙酮中，超声分散10min后备用。甲苯以3mL/min的速率输送至气液预混器，碳量子点的丙酮分散液以9mL/min的速率输送至气液预混器，氧气在气液预混器中与反应体系进行预混，控制氧气流速为250mL/min，反应体系内压为1.5MPa，后进入150℃的恒温微通道反应器进行催化氧化反应，停留时间为40min。反应后进行气液分离，气体部分主要为低浓度氧气，经处理后排空。反应后液体结晶获得苯甲酸粗品，经重结晶得到苯甲酸；其余液体经常压蒸馏、干燥、精馏得到无色油状液体产品苯甲醛，反应余液输送至预混装置进行循环。经色谱分析苯甲酸纯度为97.1％，苯甲醛纯度为98.5％，甲苯单程转化率为22.7％。
实施例59
称取10g碳量子点催化剂于5L丙酮中，超声分散10min后备用。乙苯以3mL/min的速率输送至气液预混器，碳量子点的丙酮分散液以9mL/min的速率输送至气液预混器，氧气在气液预混器中与反应体系进行预混，控制氧气流速为250mL/min，反应体系内压为1.5MPa，后进入150℃的恒温微通道反应器进 行催化氧化反应，停留时间为40min。反应后进行气液分离，气体部分主要为低浓度氧气，经处理后排空。反应后液体经常压蒸馏，收集199-203℃馏分，干燥后得到无色油状液体产品苯乙酮，反应余液输送至预混装置进行循环。经色谱分析苯乙酮纯度为97.4％，甲苯单程转化率为25.3％。
上述实施例1-28、37-59中碳量子点催化剂由粉末状石墨经多次UV辐照并研磨制得。
显然，上述实施例仅仅是为清楚地说明所作的举例，并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (10)

  1. 一种催化氧化装置，其特征在于，包括依次连通的存储单元、预混单元、微通道反应单元、气液分离单元、固液分离单元和产物纯化单元；所述存储单元用于独立存储含氧气体、原料和催化剂分散液，所述原料为单取代或双取代的苯、C4-C6链烷烃或C6-C12环烷烃，单取代或双取代的苯的取代基为C1-C4烷烃；所述产物纯化单元还通过循环管道连接至所述预混单元。
  2. 如权利要求1所述的催化氧化装置，其特征在于，所述催化剂分散液为碳基材料分散液，所述碳基材料选自碳量子点、羟基改性碳量子点、羧基改性碳量子点、羰基改性碳量子点、石墨烯、碳纳米管、金属负载碳量子点和杂原子掺杂碳量子点中的一种或多种。
  3. 如权利要求1或2所述的催化氧化装置，其特征在于，所述催化剂分散液中的溶剂为甲醇、乙醇、丙醇、丁醇、丙酮、丁酮、二氯甲烷、三氯甲烷、氯仿、乙酸乙酯、乙醚、石油醚、甲苯、二甲苯、二甲基甲酰胺、二甲基亚砜和水中的一种或多种。
  4. 如权利要求1所述的催化氧化装置，其特征在于，所述原料为正己烷、环己烷、甲苯、乙苯、金刚烷或十氢萘。
  5. 一种催化氧化方法，其特征在于，采用如权利要求1-4中任一项所述的催化氧化装置，包括以下步骤，
    S1：将存储单元存储的含氧气体、原料和催化剂分散液输送至预混单元进行预混；
    S2：经预混的含氧气体、原料和催化剂分散液进入微通道反应单元进行反应；
    S3：反应后所得气液混合物输送至气液分离单元进行分离；
    S4：分离所得的液体进入固液分离单元进行结晶，得到产物晶体；
    S5：所得产物晶体进入产物纯化单元提纯得到产物；固液分离单元内含催 化剂的溶液沿循环管道返回预混单元进入生产循环。
  6. 如权利要求5所述的催化氧化方法，其特征在于，所述预混单元和微通道反应单元内的压强为0.1-10MPa。
  7. 如权利要求5所述的催化氧化方法，其特征在于，微通道反应单元内的温度为4-300℃。
  8. 如权利要求5或7所述的催化氧化方法，其特征在于，所述步骤S2中，反应的时间为0.01-240min。
  9. 如权利要求5所述的催化氧化方法，其特征在于，催化剂分散液的浓度为0.8-2.0g/L。
  10. 如权利要求5所述的催化氧化方法，其特征在于，原料和催化剂分散液进入微通道反应单元的速率比为1：2-5。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116396273A (zh) * 2023-03-22 2023-07-07 大连理工大学 一种利用微通道反应器连续制备手性质子泵抑制剂埃索美拉唑的方法
CN116764629A (zh) * 2023-08-25 2023-09-19 内蒙古瑞翔拓创新材料有限公司 一种苯部分加氢制备环己烯钌基催化剂及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113979845A (zh) * 2021-11-18 2022-01-28 山东键兴新材料科技有限公司 一种乙苯氧化制苯乙酮生产工艺方法
CN114315583A (zh) * 2021-12-22 2022-04-12 红宝丽集团泰兴化学有限公司 一种丙烯酸酯类化合物的制备方法及其装置
CN115400712A (zh) * 2022-09-01 2022-11-29 北京慧光生物科技有限公司 一种大批量连续生产碳量子点的装置及生产方法
US20250352974A1 (en) * 2022-10-05 2025-11-20 National University Of Singapore Micro-flow synthesis of compounds and systems thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101293810A (zh) * 2007-04-28 2008-10-29 中国石油化工股份有限公司 一种环己烷的液相氧化方法
CN112569997A (zh) * 2019-09-30 2021-03-30 中国石油化工股份有限公司 纳米氮碳材料及其制备方法和环烷烃的催化氧化方法
CN112569929A (zh) * 2019-09-30 2021-03-30 中国石油化工股份有限公司 纳米碳基材料及其制备方法和环烷烃的催化氧化方法
CN113214073A (zh) * 2021-05-08 2021-08-06 中石油吉林化工工程有限公司 一种连续流微通道反应器中己二酸的合成方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105384622B (zh) * 2015-10-28 2017-08-04 江西科苑生物药业有限公司 一种环己烷氧化制己二酸的工艺方法
CN111099983A (zh) * 2018-10-29 2020-05-05 中国石油化工股份有限公司 环烃的催化氧化方法
CN109456167A (zh) * 2018-12-20 2019-03-12 福州大学 一种使用微通道反应器由环己酮合成己二酸的方法
CN110437278B (zh) * 2019-08-13 2020-08-25 南通江山农药化工股份有限公司 连续氧化制备草甘膦的方法
CN112657445A (zh) * 2020-12-11 2021-04-16 菲立化学工程(遂昌)有限公司 一种用于高放热量化学反应的连续化反应装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101293810A (zh) * 2007-04-28 2008-10-29 中国石油化工股份有限公司 一种环己烷的液相氧化方法
CN112569997A (zh) * 2019-09-30 2021-03-30 中国石油化工股份有限公司 纳米氮碳材料及其制备方法和环烷烃的催化氧化方法
CN112569929A (zh) * 2019-09-30 2021-03-30 中国石油化工股份有限公司 纳米碳基材料及其制备方法和环烷烃的催化氧化方法
CN113214073A (zh) * 2021-05-08 2021-08-06 中石油吉林化工工程有限公司 一种连续流微通道反应器中己二酸的合成方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
WANG XIAO, BIAN WENYI, MA YURONG, LIU YAN, WANG ZHENZHEN, SHI CHUNFENG, LIN HAIPING, LIU YANG, HUANG HUI, KANG ZHENHUI: "Hydroxyl-terminated carbon dots for efficient conversion of cyclohexane to adipic acid", JOURNAL OF COLLOID AND INTERFACE SCIENCE, ACADEMIC PRESS,INC., US, vol. 591, 1 June 2021 (2021-06-01), US , pages 281 - 289, XP093035144, ISSN: 0021-9797, DOI: 10.1016/j.jcis.2021.02.021 *
YU XIMENG, ZHONG-QUAN SHEN, XI-YONG DU, JI-ZHONG CHEN, ZHEJIANG: "Liquid-Phase Oxidation of Cyclohexane in a Microchannel Reactor", JOURNAL OF CHEMICAL ENGINEERING OF CHINESE UNIVERSITIES, ZHEJIANG DAXUE CAILIAO YU HUAXUE GONGCHENG XUEYUAN, CN, vol. 31, no. 6, 15 December 2017 (2017-12-15), CN , pages 1372 - 1378, XP093035143, ISSN: 1003-9015, DOI: 10.3969/j.issn.1003-9015.2017.06.016 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116396273A (zh) * 2023-03-22 2023-07-07 大连理工大学 一种利用微通道反应器连续制备手性质子泵抑制剂埃索美拉唑的方法
CN116764629A (zh) * 2023-08-25 2023-09-19 内蒙古瑞翔拓创新材料有限公司 一种苯部分加氢制备环己烯钌基催化剂及其制备方法
CN116764629B (zh) * 2023-08-25 2023-10-20 内蒙古瑞翔拓创新材料有限公司 一种苯部分加氢制备环己烯钌基催化剂及其制备方法

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