WO2013060062A1 - Gas-liquid-solid three-phase reactor and use thereof - Google Patents

Gas-liquid-solid three-phase reactor and use thereof Download PDF

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Publication number
WO2013060062A1
WO2013060062A1 PCT/CN2011/082957 CN2011082957W WO2013060062A1 WO 2013060062 A1 WO2013060062 A1 WO 2013060062A1 CN 2011082957 W CN2011082957 W CN 2011082957W WO 2013060062 A1 WO2013060062 A1 WO 2013060062A1
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gas
liquid
cylinder
liquid distribution
solid
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PCT/CN2011/082957
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French (fr)
Chinese (zh)
Inventor
陈曙光
安丽华
丁云杰
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中国科学院大连化学物理研究所
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Publication of WO2013060062A1 publication Critical patent/WO2013060062A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0453—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0492—Feeding reactive fluids
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00893—Feeding means for the reactants
    • B01J2208/00902—Nozzle-type feeding elements
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00893—Feeding means for the reactants
    • B01J2208/0092—Perforated plates

Definitions

  • the invention relates to the field of chemical engineering equipment, and in particular to a reactor in which a reaction material is a gas-liquid-solid three phase. Background technique
  • Gas-liquid-solid three-phase reactors are widely used in chemical, energy, environmental and biochemical fields. Usually a gas-liquid-solid three-phase reaction is carried out using a trickle bed or turbulent bed reactor, a mechanical stirred tank reactor, a bubble column (baffle bubble column), a rotary drum reactor or a slurry bed reaction. Device. In multiphase flow reactors, interphase mass transfer, mixing and heat transfer are important technical indicators that determine reactor performance, directly affecting reaction strength, conversion and product quality. For gas-liquid-solid three-phase reaction systems, phase-to-phase mass transfer is often a key factor in determining reactor efficiency. In particular, mass transfer is a total reaction control step and a reaction project involving a solid phase catalyst.
  • agitation In order to speed up the overall reaction process, some form of agitation must be employed to improve mass transfer efficiency and interphase mixing.
  • the use of mechanical agitation not only consumes high energy, is difficult to seal, causes environmental pollution, but also affects the stability and consistency of product quality.
  • the general bubbling bed has the advantages of simple structure, good phase contact and easy temperature adjustment, the gas pressure drop is large and the flow rate is limited.
  • the trickle bed catalyst has less stripping, uniform gas-liquid distribution, higher conversion rate and lower pressure drop, but the radial distribution of the liquid flow is not uniform during low liquid speed operation, such as channeling and bypassing, which may cause solids.
  • the catalyst is incompletely wetted and causes radial temperature non-uniformity, localized overheating, rapid catalyst deactivation and excessive vaporization of the liquid layer.
  • the disadvantage of the rotary cylinder reactor is that the particle back mixing is small, the interphase contact surface is small, the heat transfer efficiency is low, and the equipment volume is large. Summary of the invention
  • the present application aims to overcome the deficiencies of the above-mentioned prior art reactors.
  • the inventors have been engaged in the development and research of reactor equipment and industrial production practices for many years, and have provided a gas-liquid-solid three-phase reactor and its application.
  • the gas-liquid-solid three-phase reactor provided by the present application comprises a reactor cylinder; a catalyst support disk, a gas-liquid distribution plate and a liquid distribution pipe are arranged in the cylinder from the bottom to the top in the axial direction of the cylinder; the catalyst support plate And the gas-liquid distribution plate is arranged along the radial direction of the cylinder;
  • the gas-liquid distribution plate is a plate-like structure, and a hole penetrating through the upper and lower surfaces of the plate body is opened on the plate surface;
  • the liquid distribution tube is a hollow tubular structure, the surface of the tube has a small hole penetrating through the inner and outer surfaces of the tube; and the liquid distribution tube is connected to the side feed port disposed on the side wall surface of the barrel;
  • a catalyst discharge port is arranged on the side wall of the cylinder above the catalyst support plate;
  • the upper end of the cylinder body is provided with a top feed port; the lower end of the cylinder body is provided with a bottom discharge port.
  • the reactor cylinder has an aspect ratio of 2 to 12.
  • a catalyst is placed on the catalyst support disk in the cylinder, and the catalyst is located between the gas-liquid distribution plate and the catalyst support plate.
  • the number of the catalyst support disk, the gas-liquid distribution plate and the liquid distribution pipe are all 1 to 8, and the catalyst support disk, the gas-liquid distribution plate and the liquid distribution pipe are sequentially arranged from the bottom to the top in the axial direction of the cylinder. , the order of the gas-liquid distribution plate and the liquid distribution tube.
  • a dispensing cap is disposed on each opening of the gas-liquid distribution plate; the dispensing cap is placed on the surface of the gas-liquid distribution plate, and a gap is left between the dispensing cap and the upper surface of the gas-liquid distribution plate.
  • the liquid distribution pipe is composed of a main pipe and a branch pipe, and the main pipe and the branch pipe are connected, and the main pipe and the branch pipe are equidistant or not.
  • the holes are equidistantly opened; the main pipe is connected to the side feed port provided on the side wall surface of the cylinder.
  • a temperature control monitoring port and/or a pressure control monitoring port are provided on the side wall surface of the cylinder.
  • the reactor is used at a temperature of 0 to 400 ° C and a use pressure of 0 to 30.0 MPa.
  • the reactor can be used in the preparation of ethylenediamine by using ethanolamine and ammonia as raw materials under hydrogen conditions.
  • the gas-liquid-solid three-phase reactor comprises a reactor cylinder, the reactor aspect ratio is 2 to 12, preferably 5 to 10; the catalyst support disk is 1 to 8, preferably 3 to 6 per support plate, etc. Arranged in the reactor at an equidistant or unequal distance from the reactor wall at an angle of 90° to the reactor wall.
  • the diameter of the support disc is equal to the inner diameter of the reactor, and is supported by the bracket or welded to the reactor cylinder; the liquid distribution tubes are 1 to 8, Preferably, it is 3 ⁇ 6, consisting of a main pipe and a branch pipe.
  • the main pipe and the branch pipe open holes of ⁇ 2 0.1 ⁇ 10mm equidistantly or unequally; holes of ⁇ 2 5 ⁇ 100mm are opened on the gas-liquid distribution plate, preferably ⁇ 2 10 ⁇ 50mm, and add a distribution cap to each opening.
  • the distribution cap is arranged in a triangle, concentric circle, ray shape or quadrilateral.
  • the operating temperature of the reactor is between 0 ⁇ 400°C, and the operating pressure is 0 ⁇ 30.0MPa.
  • Between the side inlet ports is 1 ⁇ 8, preferably 2 ⁇ 6; the feed amount of the raw materials in different catalyst beds can be adjusted, thereby producing different reaction conversion rates and product selectivity; catalyst discharge port It is 1 to 8, preferably 3 to 6.
  • the gas-liquid-solid three-phase reactor of the invention has unique and novel structure, excellent hydrodynamic performance, adjustable reaction selectivity and conversion rate, and high total mass transfer efficiency.
  • the catalyst is packed in multiple stages in the reactor;
  • Figure 1 is a schematic view showing the structure of a gas-liquid-solid three-phase reactor
  • Figure 2 is a schematic view showing the structure of a catalyst support disk
  • Figure 3 is a schematic view showing the structure of the gas liquid distributor
  • FIG. 4 is a schematic view of the structure of the liquid distributor. detailed description
  • the present application provides a method for preparing ethylenediamine by using ethanolamine and ammonia as raw materials under the condition of hydrogen, which is combined with piperazine (PIP), aminoethylpiperazine (AEP) and hydroxyethylpiperazine (HEP). ), diethylene triamine (DETA), hydroxyethyl ethylene diamine (AEEA), and the like.
  • PIP piperazine
  • AEP aminoethylpiperazine
  • HEP hydroxyethylpiperazine
  • DETA diethylene triamine
  • AEEA hydroxyethyl ethylene diamine
  • the reaction system consists of ethanolamine, ammonia, hydrogen and a catalyst.
  • the height of the reactor cylinder is 1200mm and the diameter is 500mm.
  • the inside is equipped with a two-layer liquid distribution pipe 3, which has holes of ⁇ 20.5mm and ⁇ 22.0mm, two layers of gas-liquid distributor 4 and 110 distribution caps, and distribution caps.
  • a two-layer liquid distribution pipe 3 which has holes of ⁇ 20.5mm and ⁇ 22.0mm, two layers of gas-liquid distributor 4 and 110 distribution caps, and distribution caps.
  • two layers of catalyst support discs 2 Arranged in an equilateral triangle, two layers of catalyst support discs 2 with a spacing of 300 mm.
  • the reactor cylinder 1 is sequentially disposed in the axial direction of the cylinder from bottom to top in order of the catalyst support disk 2, the gas-liquid distribution plate 4, the liquid distribution pipe 3, the catalyst support disk 2, the gas-liquid distribution plate 4, and the liquid distribution pipe 3;
  • the catalyst support disk 2, the liquid distribution pipe 3 and the gas-liquid distribution plate 4 are arranged along the radial direction of the cylinder;
  • the gas-liquid distribution plate 4 is a plate-like structure, and a hole penetrating through the upper and lower surfaces of the plate body is opened on the plate surface; a catalyst is placed on the catalyst support disk 2 in the cylinder body 1, and the catalyst is located on the gas-liquid distribution plate 4 and the catalyst support plate 2 rooms.
  • the gas-liquid distribution plate 3 is equidistantly opened; arranged in a diamond shape.
  • a dispensing cap 5 is disposed on each opening of the gas-liquid distribution tray 4; the dispensing cap 5 is fastened to the upper surface of the gas-liquid distribution tray 4, and a gap is left between the dispensing cap 5 and the upper surface of the gas-liquid distribution tray 4. .
  • the liquid distribution pipe 3 is composed of a main pipe and a branch pipe, and the main pipe and the branch pipe are connected, and the main pipe and the branch pipe are equidistantly or unequally opened; the main pipe is connected to the side feed port 9 provided on the side wall surface of the cylinder body 1.
  • a temperature control monitoring port 6 and/or a pressure control monitoring port 7 are provided on the side wall surface of the cylinder 1.
  • the equipment process conditions are as follows:
  • the reaction temperature was 155 ° C
  • the reaction pressure was 8.0 MPa
  • the ammonia/ethanolamine molar ratio was 10
  • the hydrogen/ethanolamine molar ratio was 0.015
  • the ethanolamine liquid space velocity was 0.5 h.
  • the catalyst was prepared by the preparation method reported in the invention patent CN101704753A.
  • the catalyst particle size is between ⁇ 2 ⁇ 3mm, and the catalyst is put into the reactor in a single time.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A gas-liquid-solid three-phase reactor, comprising a reactor cylinder (1) with a catalyst support disc (2), a gas-liquid dispensing disc (4) and a liquid distributing pipe (3) provided inside the cylinder (1) in succession from bottom to top along the cylinder (1), wherein the catalyst support disc (2), the liquid distributing pipe (3) and the gas-liquid dispensing disc (4) are arranged radially along the cylinder (1); the gas-liquid dispensing disc (4) has a plate-like structure, provided with holes extending through the top and bottom surfaces of the plate; the liquid distributing pipe (3) has a hollow tubular structure, the surface of the pipe being provided with small holes extending through the inner and outer surfaces of the pipe body, the liquid distributing pipe (3) being connected with a lateral feed port (9) provided on the side wall face of the cylinder (1); the side wall face of the cylinder (1) above the catalyst support disc (2) is provided with a catalyst discharge port (11); and a top feed port (8) is provided at the top of the cylinder (1) and a bottom discharge port (10) is provided at the bottom of the cylinder (1). The reactor is suitable for a gas-liquid-solid three-phase reaction at a temperature of 0 - 400°C, and a pressure of 0 - 30.0 MPa, and can be used in the reaction for preparing ethylenediamine with ethanolamine and ammonia as raw materials in the presence of hydrogen.

Description

一种气-液-固三相反应器及其应用 技术领域  Gas-liquid-solid three-phase reactor and application thereof
本发明涉及一种化学工程设备领域， 具体涉及一种反应物料为气-液 -固三相的反 应器。 背景技术  The invention relates to the field of chemical engineering equipment, and in particular to a reactor in which a reaction material is a gas-liquid-solid three phase. Background technique
气-液 -固三相反应器广泛应用于化工、 能源、 环境和生化等领域。 通常对气-液- 固三相反应采用滴流床或称涓流床反应器， 机械搅拌釜式反应器、鼓泡塔（挡板鼓泡 塔）、 回转筒式反应器或於浆床反应器。 在多相流的反应器中， 相间传质、 混合和传 热是决定反应器性能的重要技术指标， 直接影响到反应强度、转化率和产品质量。对 于气-液 -固三相反应体系， 相间传质往往是决定反应器效率的关键因素。 特别是对于 传质是总反应控制步骤和涉及固相催化剂的反应工程， 为加快总反应过程，就必须采 取某种形式的搅拌， 以提高传质效率和相间混合。 采用机械搅拌， 不仅能耗高， 不易 密封， 造成环境污染， 而且产品质量的稳定性和一致性也受到影响。 一般的鼓泡床虽 然具有结构简单， 相间接触好、 温度易调节的优点， 但气体压降大， 流速有限制。 滴 流床催化剂带出少， 气-液分布均匀， 可以获得较高的转化率， 压降小， 但低液速操 作时液流径向分布不均匀， 如沟流、 旁路， 可能引起固体催化剂润湿不完全， 并且引 起径向温度不均匀， 形成局部过热， 使催化剂迅速失活并使液层过量汽化。 回转筒式 反应器缺点是粒子返混小， 相间接触面小， 传热效能低， 设备容积较大。 发明内容  Gas-liquid-solid three-phase reactors are widely used in chemical, energy, environmental and biochemical fields. Usually a gas-liquid-solid three-phase reaction is carried out using a trickle bed or turbulent bed reactor, a mechanical stirred tank reactor, a bubble column (baffle bubble column), a rotary drum reactor or a slurry bed reaction. Device. In multiphase flow reactors, interphase mass transfer, mixing and heat transfer are important technical indicators that determine reactor performance, directly affecting reaction strength, conversion and product quality. For gas-liquid-solid three-phase reaction systems, phase-to-phase mass transfer is often a key factor in determining reactor efficiency. In particular, mass transfer is a total reaction control step and a reaction project involving a solid phase catalyst. In order to speed up the overall reaction process, some form of agitation must be employed to improve mass transfer efficiency and interphase mixing. The use of mechanical agitation not only consumes high energy, is difficult to seal, causes environmental pollution, but also affects the stability and consistency of product quality. Although the general bubbling bed has the advantages of simple structure, good phase contact and easy temperature adjustment, the gas pressure drop is large and the flow rate is limited. The trickle bed catalyst has less stripping, uniform gas-liquid distribution, higher conversion rate and lower pressure drop, but the radial distribution of the liquid flow is not uniform during low liquid speed operation, such as channeling and bypassing, which may cause solids. The catalyst is incompletely wetted and causes radial temperature non-uniformity, localized overheating, rapid catalyst deactivation and excessive vaporization of the liquid layer. The disadvantage of the rotary cylinder reactor is that the particle back mixing is small, the interphase contact surface is small, the heat transfer efficiency is low, and the equipment volume is large. Summary of the invention
本申请目的在于克服上述现有技术中的反应器存在的不足，经发明人多年从事反 应器设备的开发研究及工业化生产实践， 提供一种气-液 -固三相反应器及其应用。  The present application aims to overcome the deficiencies of the above-mentioned prior art reactors. The inventors have been engaged in the development and research of reactor equipment and industrial production practices for many years, and have provided a gas-liquid-solid three-phase reactor and its application.
本申请提供的气-液-固三相反应器， 包括反应器筒体； 筒体内沿筒体的轴向从下 至上依次设置有催化剂支撑盘、气液分配盘和液体分布管； 催化剂支撑盘和气液分配 盘沿筒体的径向设置；  The gas-liquid-solid three-phase reactor provided by the present application comprises a reactor cylinder; a catalyst support disk, a gas-liquid distribution plate and a liquid distribution pipe are arranged in the cylinder from the bottom to the top in the axial direction of the cylinder; the catalyst support plate And the gas-liquid distribution plate is arranged along the radial direction of the cylinder;
气液分配盘为一板状结构， 板面上开设有贯通板体上下表面的孔；  The gas-liquid distribution plate is a plate-like structure, and a hole penetrating through the upper and lower surfaces of the plate body is opened on the plate surface;
液体分布管为中空的管状结构， 管的表面带有贯通管体内外表面的小孔； 液体分 布管与设置于筒体侧壁面上的侧面进料口相连；  The liquid distribution tube is a hollow tubular structure, the surface of the tube has a small hole penetrating through the inner and outer surfaces of the tube; and the liquid distribution tube is connected to the side feed port disposed on the side wall surface of the barrel;
催化剂支撑盘上方的、 筒体侧壁面上设有催化剂卸料口；  a catalyst discharge port is arranged on the side wall of the cylinder above the catalyst support plate;
筒体上端设有顶部进料口； 筒体下端设有底部出料口。  The upper end of the cylinder body is provided with a top feed port; the lower end of the cylinder body is provided with a bottom discharge port.
所述反应器筒体的长径比为 2〜12。 于筒体内的催化剂支撑盘上放置有催化剂， 催化剂位于气液分配盘与催化剂支撑盘间。  The reactor cylinder has an aspect ratio of 2 to 12. A catalyst is placed on the catalyst support disk in the cylinder, and the catalyst is located between the gas-liquid distribution plate and the catalyst support plate.
所述催化剂支撑盘、气液分配盘和液体分布管数量均为 1〜8个，沿筒体的轴向从 下至上依次按催化剂支撑盘、气液分配盘和液体分布管……催化剂支撑盘、气液分配 盘和液体分布管的顺序设置。  The number of the catalyst support disk, the gas-liquid distribution plate and the liquid distribution pipe are all 1 to 8, and the catalyst support disk, the gas-liquid distribution plate and the liquid distribution pipe are sequentially arranged from the bottom to the top in the axial direction of the cylinder. , the order of the gas-liquid distribution plate and the liquid distribution tube.
所述气液分配盘的每个开孔上都设有一个分配帽；分配帽扣置于气液分配盘上表 面， 分配帽与气液分配盘上表面间留有间隙。  A dispensing cap is disposed on each opening of the gas-liquid distribution plate; the dispensing cap is placed on the surface of the gas-liquid distribution plate, and a gap is left between the dispensing cap and the upper surface of the gas-liquid distribution plate.
所述液体分布管由主管和支管组成， 主管和支管相连通， 主管和支管上等距或不 等距地开孔； 主管与设置于筒体侧壁面上的侧面进料口相连。 The liquid distribution pipe is composed of a main pipe and a branch pipe, and the main pipe and the branch pipe are connected, and the main pipe and the branch pipe are equidistant or not. The holes are equidistantly opened; the main pipe is connected to the side feed port provided on the side wall surface of the cylinder.
于筒体侧壁面上设有温度控制监测口和 /或压力控制监测口。  A temperature control monitoring port and/or a pressure control monitoring port are provided on the side wall surface of the cylinder.
所述反应器的使用温度为 0〜400°C， 使用压力为 0〜30.0MPa。  The reactor is used at a temperature of 0 to 400 ° C and a use pressure of 0 to 30.0 MPa.
反应器可用于以乙醇胺和氨为原料临氢条件下制备乙二胺反应中。  The reactor can be used in the preparation of ethylenediamine by using ethanolamine and ammonia as raw materials under hydrogen conditions.
气-液 -固三相反应器包括反应器筒体， 反应器长径比为 2〜12， 优选为 5〜10； 催 化剂支撑盘为 1〜8块， 优选为 3〜6 每块支撑盘等距或不等距地设置在反应器内， 与 反应器壁成 90° 角， 支撑盘的直径等于反应器内径， 通过支架或焊接在反应器筒体 上； 液体分布管为 1〜8个， 优选为 3〜6个 ， 由主管和支管组成， 主管和支管等距或 不等距地开 <2 0.1〜10mm 的孔； 气液分配盘上开 <2 5〜100mm 的孔， 优选为 <2 10〜50mm ， 并在每个开孔上加装分配帽， 分配帽呈三角形、 同心圆、 射线形或四边 形排列； 反应器操作温度在 0〜400°C之间， 操作压力在 0〜30.0MPa之间； 侧面进料口 为 1〜8个， 优选为 2〜6个 ； 可以调节原料在不同催化剂床层的进料量， 进而产生不 同的反应转化率和产品的选择性； 催化剂卸料口为 1〜8个， 优选为 3〜6。  The gas-liquid-solid three-phase reactor comprises a reactor cylinder, the reactor aspect ratio is 2 to 12, preferably 5 to 10; the catalyst support disk is 1 to 8, preferably 3 to 6 per support plate, etc. Arranged in the reactor at an equidistant or unequal distance from the reactor wall at an angle of 90° to the reactor wall. The diameter of the support disc is equal to the inner diameter of the reactor, and is supported by the bracket or welded to the reactor cylinder; the liquid distribution tubes are 1 to 8, Preferably, it is 3~6, consisting of a main pipe and a branch pipe. The main pipe and the branch pipe open holes of <2 0.1~10mm equidistantly or unequally; holes of <2 5~100mm are opened on the gas-liquid distribution plate, preferably <2 10~50mm, and add a distribution cap to each opening. The distribution cap is arranged in a triangle, concentric circle, ray shape or quadrilateral. The operating temperature of the reactor is between 0~400°C, and the operating pressure is 0~30.0MPa. Between the side inlet ports is 1~8, preferably 2~6; the feed amount of the raw materials in different catalyst beds can be adjusted, thereby producing different reaction conversion rates and product selectivity; catalyst discharge port It is 1 to 8, preferably 3 to 6.
本发明气-液-固三相反应器结构独特新颖， 流体力学性能优良、 反应选择性和转 化率可调、 总传质效率高。  The gas-liquid-solid three-phase reactor of the invention has unique and novel structure, excellent hydrodynamic performance, adjustable reaction selectivity and conversion rate, and high total mass transfer efficiency.
本申请具有以下优点：  This application has the following advantages:
( 1 ) 反应器中催化剂多段装填；  (1) The catalyst is packed in multiple stages in the reactor;
(2) 原料分多股进料；  (2) The raw materials are divided into multiple feeds;
(3 ) 床层压差小；  (3) The bed lamination is small;
(4) 反应转化率和产品的选择性可调。 附图说明  (4) The reaction conversion rate and the selectivity of the product are adjustable. DRAWINGS
下面结合附图对本申请进行进一步的说明。  The present application will be further described below in conjunction with the accompanying drawings.
图 1是气 -液-固三相反应器结构示意图；  Figure 1 is a schematic view showing the structure of a gas-liquid-solid three-phase reactor;
图 2催化剂支撑盘结构示意图；  Figure 2 is a schematic view showing the structure of a catalyst support disk;
图 3气液体分布器结构示意图；  Figure 3 is a schematic view showing the structure of the gas liquid distributor;
图 4液体分布器结构示意图。 具体实施方式  Figure 4 is a schematic view of the structure of the liquid distributor. detailed description
本申请提供了一种以乙醇胺和氨为原料在临氢条件下制备乙二胺的方法，该过程 联产哌嗪 （PIP)、 氨乙基哌嗪 （AEP)、 羟乙基哌嗪 （HEP)、 二乙烯三胺 （DETA)、 羟乙基乙二胺 （AEEA) 等。 反应体系由乙醇胺、 氨、 氢气和催化剂组成。  The present application provides a method for preparing ethylenediamine by using ethanolamine and ammonia as raw materials under the condition of hydrogen, which is combined with piperazine (PIP), aminoethylpiperazine (AEP) and hydroxyethylpiperazine (HEP). ), diethylene triamine (DETA), hydroxyethyl ethylene diamine (AEEA), and the like. The reaction system consists of ethanolamine, ammonia, hydrogen and a catalyst.
用下列实施例来进一步说明本发明， 但本发明的保护范围并不限于下列实施例 子。  The invention is further illustrated by the following examples, but the scope of the invention is not limited to the following examples.
实施例 1  Example 1
采用图 1的设备、 图 2的催化剂支撑盘、 图 3的气液体分布器和图 4的液体分布 器。  The apparatus of Fig. 1, the catalyst support disk of Fig. 2, the gas liquid distributor of Fig. 3, and the liquid distributor of Fig. 4 were employed.
反应器筒体高度为 1200mm， 直径为 500mm， 内部装有二层液体分布管 3， 其上 开 <20.5mm及 <22.0mm的孔、二层气液分布器 4及 110个分配帽，分配帽呈正三角形 排列、 二层催化剂支撑盘 2， 间距为 300mm。 反应器筒体 1内沿筒体的轴向从下至上依次按催化剂支撑盘 2、 气液分配盘 4、 液体分布管 3、 催化剂支撑盘 2气液分配盘 4和液体分布管 3顺序设置； 催化剂支撑 盘 2、 液体分布管 3和气液分配盘 4沿筒体的径向设置； The height of the reactor cylinder is 1200mm and the diameter is 500mm. The inside is equipped with a two-layer liquid distribution pipe 3, which has holes of <20.5mm and <22.0mm, two layers of gas-liquid distributor 4 and 110 distribution caps, and distribution caps. Arranged in an equilateral triangle, two layers of catalyst support discs 2 with a spacing of 300 mm. The reactor cylinder 1 is sequentially disposed in the axial direction of the cylinder from bottom to top in order of the catalyst support disk 2, the gas-liquid distribution plate 4, the liquid distribution pipe 3, the catalyst support disk 2, the gas-liquid distribution plate 4, and the liquid distribution pipe 3; The catalyst support disk 2, the liquid distribution pipe 3 and the gas-liquid distribution plate 4 are arranged along the radial direction of the cylinder;
气液分配盘 4为一板状结构， 板面上开设有贯通板体上下表面的孔； 于筒体 1内的催化剂支撑盘 2上放置有催化剂，催化剂位于气液分配盘 4与催化 剂支撑盘 2间。  The gas-liquid distribution plate 4 is a plate-like structure, and a hole penetrating through the upper and lower surfaces of the plate body is opened on the plate surface; a catalyst is placed on the catalyst support disk 2 in the cylinder body 1, and the catalyst is located on the gas-liquid distribution plate 4 and the catalyst support plate 2 rooms.
所述气液分配盘 3等距开孔； 呈菱形排列。  The gas-liquid distribution plate 3 is equidistantly opened; arranged in a diamond shape.
所述气液分配盘 4的每个开孔上都设有一个分配帽 5 ; 分配帽 5扣置于气液分配 盘 4上表面， 分配帽 5与气液分配盘 4上表面间留有间隙。  A dispensing cap 5 is disposed on each opening of the gas-liquid distribution tray 4; the dispensing cap 5 is fastened to the upper surface of the gas-liquid distribution tray 4, and a gap is left between the dispensing cap 5 and the upper surface of the gas-liquid distribution tray 4. .
所述液体分布管 3由主管和支管组成， 主管和支管相连通， 主管和支管上等距或 不等距地开孔； 主管与设置于筒体 1侧壁面上的侧面进料口 9相连。  The liquid distribution pipe 3 is composed of a main pipe and a branch pipe, and the main pipe and the branch pipe are connected, and the main pipe and the branch pipe are equidistantly or unequally opened; the main pipe is connected to the side feed port 9 provided on the side wall surface of the cylinder body 1.
于筒体 1侧壁面上设有温度控制监测口 6和 /或压力控制监测口 7。  A temperature control monitoring port 6 and/or a pressure control monitoring port 7 are provided on the side wall surface of the cylinder 1.
设备工艺条件如下：  The equipment process conditions are as follows:
反应温度为 155 °C， 反应压力为 8.0MPa， 氨 /乙醇胺摩尔比为 10， 氢气 /乙醇胺摩 尔比为 0.015， 乙醇胺液体空速为 0.5h- 催化剂采用发明专利 CN101704753A报道的制备方法制备。 催化剂颗粒度在 Φ 2〜3mm之间， 催化剂为先期一次性投入反应器内。  The reaction temperature was 155 ° C, the reaction pressure was 8.0 MPa, the ammonia/ethanolamine molar ratio was 10, the hydrogen/ethanolamine molar ratio was 0.015, and the ethanolamine liquid space velocity was 0.5 h. The catalyst was prepared by the preparation method reported in the invention patent CN101704753A. The catalyst particle size is between Φ 2~3mm, and the catalyst is put into the reactor in a single time.
先将氢气通入反应器， 通过加热氢气使反应器提温、 提压， 温度、 压力分别达到 150°C、 8.0MPa后逐步加入液氨， 待温度稳定后， 加入原料乙醇胺， 乙醇胺的单程转 化率可达到 50%， 乙二胺的选择性可达到 80%。  First, hydrogen is introduced into the reactor, and the reactor is heated and pressurized by heating hydrogen. The temperature and pressure are respectively 150 ° C and 8.0 MPa, and then liquid ammonia is gradually added. After the temperature is stabilized, the raw material ethanolamine and the ethanolamine are converted into a single pass. The rate can reach 50%, and the selectivity of ethylenediamine can reach 80%.

Claims

权 利 要 求 书 Claim
1. 一种气-液-固三相反应器， 其特征在于： 包括反应器筒体 （1); 筒体 （1) 内 沿筒体的轴向从下至上依次设置有催化剂支撑盘 （2)、 气液分配盘 （4) 和液体分布 管（3); 催化剂支撑盘（2)、液体分布管（3)和气液分配盘（4)沿筒体的径向设置; 气液分配盘 （4) 为一板状结构， 板面上开设有贯通板体上下表面的孔； 液体分布管 （3) 为中空的管状结构， 管的表面带有贯通管体内外表面的小孔； 液体分布管 （3) 与设置于筒体 （1) 侧壁面上的侧面进料口 （9) 相连； A gas-liquid-solid three-phase reactor, comprising: a reactor cylinder (1); a cylindrical support body (1) is provided with a catalyst support disk in the axial direction of the cylinder from bottom to top (2) ), gas-liquid distribution plate (4) and liquid distribution pipe (3); catalyst support plate (2), liquid distribution pipe (3) and gas-liquid distribution plate (4) are arranged along the radial direction of the cylinder; gas-liquid distribution plate ( 4) is a plate-like structure, the plate surface is provided with a hole penetrating the upper and lower surfaces of the plate body; the liquid distribution pipe (3) is a hollow tubular structure, and the surface of the pipe has a small hole penetrating the inner and outer surfaces of the pipe; the liquid distribution pipe (3) connected to the side feed port (9) provided on the side wall surface of the cylinder (1);
催化剂支撑盘 （2) 上方的、 筒体 （1) 侧壁面上设有催化剂卸料口 （11);  Above the catalyst support plate (2), the cylinder body (1) is provided with a catalyst discharge port (11) on the side wall surface;
筒体 （1) 上端设有顶部进料口 （8); 筒体 （1) 下端设有底部出料口 （10)。 The upper end of the cylinder (1) is provided with a top feed port (8); the lower end of the cylinder body (1) is provided with a bottom discharge port (10).
2. 根据权利要求 1 所述的气-液-固三相反应器， 其特征在于： 所述反应器筒体 (1) 的长径比为 2〜12； 2. The gas-liquid-solid three-phase reactor according to claim 1, wherein: the reactor cylinder (1) has an aspect ratio of 2 to 12;
于筒体（1)内的催化剂支撑盘（2)上放置有催化剂，催化剂位于气液分配盘（4) 与催化剂支撑盘 （2) 间。  A catalyst is placed on the catalyst support disk (2) in the cylinder (1), and the catalyst is located between the gas-liquid distribution plate (4) and the catalyst support plate (2).
3. 根据权利要求 1所述的气-液-固三相反应器， 其特征在于： 所述支撑盘 （2) 与反应器筒体 （1) 的内壁成 90° 角， 直径等于反应器内径， 通过支架或焊接固定在 反应器筒体 （1) 内壁上；  The gas-liquid-solid three-phase reactor according to claim 1, characterized in that: the support disk (2) is at an angle of 90° to the inner wall of the reactor cylinder (1), and the diameter is equal to the inner diameter of the reactor , fixed to the inner wall of the reactor cylinder (1) by bracket or welding;
所述催化剂支撑盘 （2) 的数量为 1〜8个， 支撑盘之间等距或不等距地固定在反 应器筒体 （1) 的内壁上。  The number of the catalyst support discs (2) is 1 to 8, and the support discs are fixed equidistantly or unequally between the inner walls of the reactor cylinder (1).
4. 根据权利要求 1 所述的气-液-固三相反应器， 其特征在于： 所述气液分布盘 (3) 与反应器筒体 （1) 的内壁成 90° 角， 数量为 1〜8个， 各个分配盘之间等距或 不等距地固定在反应器筒体 （1) 的内壁上；  4. The gas-liquid-solid three-phase reactor according to claim 1, wherein: the gas-liquid distribution plate (3) is at an angle of 90 to the inner wall of the reactor cylinder (1), and the number is one. ~8, each distribution disc is fixed equidistantly or unequally on the inner wall of the reactor cylinder (1);
所述气液分配盘（3)等距或不等距地开孔； 所述气液分配盘（4)上的孔直径为 5〜100mm， 呈三角形、 同心圆、 射线形、 菱形、 四边形或正方形排列。  The gas-liquid distribution plate (3) is opened at equal or unequal distances; the hole on the gas-liquid distribution plate (4) has a diameter of 5 to 100 mm, and is triangular, concentric, ray-shaped, rhomboid, quadrangular or Arranged in squares.
5. 根据权利要求 1、 3或 4所述的气-液-固三相反应器， 其特征在于： 所述催化剂支撑盘 （2)、 气液分配盘 （4) 和液体分布管 （3) 数量均为 2〜8个， 沿筒体的轴向从下至上依次按催化剂支撑盘 （2)、 气液分配盘 （4) 和液体分布管 The gas-liquid-solid three-phase reactor according to claim 1, 3 or 4, characterized in that: the catalyst support disk (2), the gas-liquid distribution plate (4) and the liquid distribution pipe (3) The number is 2~8, according to the axial direction of the cylinder, the catalyst support plate (2), the gas-liquid distribution plate (4) and the liquid distribution pipe are sequentially arranged from bottom to top.
(3) ……催化剂支撑盘 （2)、 气液分配盘 （4) 和液体分布管 （3) 的顺序设置。 (3) ... The order of the catalyst support plate (2), the gas-liquid distribution plate (4) and the liquid distribution pipe (3).
6. 根据权利要求 1 所述的气-液-固三相反应器， 其特征在于： 所述气液分配盘 6. The gas-liquid-solid three-phase reactor according to claim 1, wherein: the gas-liquid distribution plate
(4) 的每个开孔上都设有一个分配帽 （5); 分配帽 （5) 扣置于气液分配盘 （4) 表 面的开孔上， 分配帽 （5) 与气液分配盘 （4) 上表面间留有间隙。 (4) Each of the openings is provided with a dispensing cap (5); the dispensing cap (5) is attached to the opening of the surface of the gas-liquid distribution plate (4), the dispensing cap (5) and the gas-liquid distribution plate (4) There is a gap between the upper surfaces.
7. 根据权利要求 1 所述的气-液-固三相反应器， 其特征在于： 所述液体分布管 (3) 由主管和支管组成， 主管和支管相连通， 主管和支管上等距或不等距地开孔； 主管与设置于筒体 （1) 侧壁面上的侧面进料口 （9) 相连。  7. The gas-liquid-solid three-phase reactor according to claim 1, wherein: the liquid distribution pipe (3) is composed of a main pipe and a branch pipe, and the main pipe and the branch pipe are connected, and the main pipe and the branch pipe are equidistant or Opening the holes unequally; the main pipe is connected to the side feed port (9) provided on the side wall surface of the cylinder (1).
8. 根据权利要求 1、 3或 4所述的一种气-液-固三相反应器， 其特征在于： 侧面 进料口 （9) 为 1〜8个， 催化剂卸料口 （11) 为 1〜8个。  8. A gas-liquid-solid three-phase reactor according to claim 1, 3 or 4, characterized in that: the side feed ports (9) are 1 to 8, and the catalyst discharge port (11) is 1 to 8 pieces.
9. 根据权利要求 1所述的气-液-固三相反应器， 其特征在于： 于筒体 （1) 侧壁 面上设有温度控制监测口 （6) 和 /或压力控制监测口 （7)。  9. The gas-liquid-solid three-phase reactor according to claim 1, characterized in that: a temperature control monitoring port (6) and/or a pressure control monitoring port are provided on the side wall surface of the cylinder (1) (7) ).
10. 一种权利要求 1-9任一所述的气-液-固三相反应器的应用， 其特征在于： 反 应器的使用温度为 0〜400°C， 使用压力为 0〜30.0MPa。 10. Use of a gas-liquid-solid three-phase reactor according to any of claims 1-9, characterized in that the reactor is used at a temperature of from 0 to 400 ° C and a pressure of from 0 to 30.0 MPa.
11. 按照权利要求 10 所述的气-液-固三相反应器的应用， 其特征在于： 反应器 用于以乙醇胺和氨为原料临氢条件下制备乙二胺反应中。 11. The use of a gas-liquid-solid three-phase reactor according to claim 10, wherein: the reactor is used for the preparation of ethylenediamine by using ethanolamine and ammonia as raw materials under hydrogen conditions.
PCT/CN2011/082957 2011-10-27 2011-11-25 Gas-liquid-solid three-phase reactor and use thereof WO2013060062A1 (en)

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