WO2024065074A1 - Dynamic combined micro-channel continuous flow reactor - Google Patents

Dynamic combined micro-channel continuous flow reactor Download PDF

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Publication number
WO2024065074A1
WO2024065074A1 PCT/CN2022/121198 CN2022121198W WO2024065074A1 WO 2024065074 A1 WO2024065074 A1 WO 2024065074A1 CN 2022121198 W CN2022121198 W CN 2022121198W WO 2024065074 A1 WO2024065074 A1 WO 2024065074A1
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WIPO (PCT)
Prior art keywords
reaction tube
rotating shaft
baffle
heat exchanger
baffles
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PCT/CN2022/121198
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French (fr)
Chinese (zh)
Inventor
叶伟平
周宏宇
费安杰
王扬
吴杰
傅利
罗富元
林柳君
周章涛
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广东莱佛士制药技术有限公司
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Priority to PCT/CN2022/121198 priority Critical patent/WO2024065074A1/en
Publication of WO2024065074A1 publication Critical patent/WO2024065074A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers

Definitions

  • the invention relates to the field of continuous flow reaction devices, in particular to a dynamic mixing microchannel continuous flow reactor.
  • Common microchannel reactors are planar structures and belong to static mixers. Although they have good mass transfer and heat exchange effects, their solid content carrying capacity for the reactor is relatively weak (generally, the solid loading must be less than 10%, and the solid particle size must be less than 0.5 mm). For tubular reactors with relatively good solid content carrying capacity, their mass transfer effect is poor, and the larger the tube diameter, the worse the mass transfer and heat transfer effect, and the more obvious the amplification effect, resulting in low production efficiency. Even if the tubular reactor is designed in the form of dynamic rotating shaft mixing, turbulence is increased, and the mass transfer effect is enhanced, its mass transfer and heat transfer effect is still far from that of the traditional microchannel continuous flow reactor.
  • the conventional continuous flow reactor has strong specificity and weak universality, and production equipment needs to be customized for different processes, and the related investment is high. Therefore, the industry is in urgent need of a type of continuous flow reactor with strong process universality and can be assembled quickly.
  • the purpose of the present invention is to provide a dynamic mixing microchannel continuous flow reactor, aiming to solve the shortcomings of low solid loading capacity of microchannels, easy channel clogging, poor mixing effect and weak heat exchange capacity of common tubular reactors, so as to achieve one reactor to cover multiple reaction types, increase equipment utilization, improve production efficiency and reduce production costs.
  • the present invention is implemented through the following technical solutions:
  • the inner curved surface of the reaction tube and the rotating shaft are designed as a continuous multi-level structure with uneven surfaces.
  • the inner wall of the reaction tube and the rotating shaft are nested with each other to form a tiny reaction channel.
  • the rotating shaft provides lateral shear force as the driving force for dynamic mixing.
  • the reaction tube is designed as a two-in-one split structure. On the one hand, it is easy to disassemble and repair. On the other hand, higher protrusions can be designed on the inner surface of the reaction tube and the surface of the rotating shaft, so that a smaller microchannel can be formed, further enhancing the mass transfer effect.
  • the rotating shaft is designed to be a multi-tooth structure with high and low protrusions, the height of the high protrusion is 3.0-20.0 mm, the height of the concave part is 1.0-3.0 mm, and the overall concave part is nested with the protrusion of the reaction tube to allow fluid to pass through, and it is a multi-tooth structure when viewed from the side;
  • the main body of the reaction tube is a reactant container cavity, which is a split structure and can be divided into two. There is a sealing gasket at the joint.
  • the inner wall of the container cavity is designed as a split-type continuous flow multi-stage structure.
  • the protruding part is used as a baffle.
  • the height of the baffle is between 3.0 and 20.0 mm.
  • the depth of the concave structure here is 1.00 to 3.00 mm.
  • the distance between the top of the rotating shaft protrusion and the bottom of the overall depression of the reaction tube is between 1.0 and 3.0 mm, and the distance between the top of the reaction tube protrusion and the bottom of the overall depression of the rotating shaft is between 1.0 and 3.0 mm;
  • a detachable, split-type return flow channel type jacket heat exchanger is used outside the reaction tube, which can be divided into two parts, with a sealing gasket at the joint, and is integrated with the reaction tube by overlapping with fixing bolts.
  • the groove inside the heat exchanger is tightly fitted with the outer wall of the reaction tube to form a heat exchange passage;
  • Both ends of the reaction tube are composed of quick-release flanges, which are used for overall sealing, as well as bearing mechanical seals and fixing the rotating shaft;
  • the driving device adopts a servo motor or a pneumatic motor to drive the rotating shaft to rotate, and can realize multi-level speed adjustment.
  • the beneficial effect of the present invention lies in that the present invention adopts a unique structural design, namely: on the one hand, the reactor pipe size adopted by the present invention is the size of a common tubular reactor, and a micro-reaction channel is formed in the reaction tube through the inner wall of the tube and the concave baffle structure on the rotating shaft, thereby greatly improving the mass transfer and heat transfer efficiency of the tubular reactor, and at the same time having the advantages of high mass transfer efficiency of the microchannel continuous flow reactor and large flux of the tubular reactor, but avoiding the disadvantages of low solid carrying capacity of the microchannel reactor and poor mass transfer and heat transfer of the conventional tubular reactor.
  • the reaction tube is designed as a split structure, which is convenient for disassembly and assembly, and thus the concave baffle structure on the inner wall of the tube and the convex structure on the rotating shaft can be designed to be larger in size, so that a smaller microchannel can be formed, back-mixing phenomenon can be avoided, and the mass transfer effect is further enhanced.
  • FIG1 is an exploded view of a dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention.
  • FIG2 is a schematic diagram of the overall structure of a dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention.
  • FIG 3 is a longitudinal cross-sectional view of the overall structure of a dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention.
  • FIG. 4 is a schematic diagram of the structure of a heat exchanger in a dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention.
  • FIG5 is a schematic diagram of the reaction tube structure in a dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention.
  • FIG6 is a schematic diagram of the structure of the rotating shaft in the dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention.
  • FIG. 7 is a schematic diagram of the flange cover structure in a dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention.
  • orientation or positional relationship indicated by the terms “length”, “width”, “upper”, “lower”, “far”, “near”, etc. is based on the orientation or positional relationship shown in the drawings, which is only for the convenience of describing the invention and simplifying the description, and does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and cannot be understood as limiting the specific protection scope of the invention.
  • first and second are only used for descriptive purposes to distinguish technical features, and do not have substantial meanings, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features.
  • the dynamic mixing microchannel continuous flow reactor includes a reaction tube, a rotating shaft 30, a first heat exchanger 10 and a second heat exchanger 11, a coupling 60 and a driving device 70.
  • the reaction tube includes a first half reaction tube 20 and a second half reaction tube 21, the inner diameter of the reaction tube is greater than the outer diameter of the rotating shaft 30, the rotating shaft 30 is coaxially arranged inside the reaction tube 20, and the driving device 70 is configured to be able to drive the rotating shaft 30 to rotate relative to the reaction tube.
  • the first half reaction tube 20 and the second half reaction tube 21 are two semi-cylinders of the same shape and size, and the two are assembled together to form a reaction tube with a cylindrical space inside (see Figure 4).
  • the first half reaction tube 20 and the second half reaction tube 21 are fixed as a whole by bolts in the transverse position, and the radial fitting surfaces of the two are provided with PTFE sealing gaskets.
  • At least one stopper is provided on the inner surface of the reaction tube formed by the first half reaction tube 20 and the second half reaction tube 21.
  • the stopper is in a circular shape and close to the inner surface of the reaction tube.
  • the height of the at least one stopper on the inner surface of the reaction tube is between 3.0 and 20.0 mm.
  • At least one depression is provided on the stopper, and the depth of the depression is 1.00 to 3.00 mm.
  • at least one stopper is provided on the rotating shaft 30.
  • the stopper is in a circular shape and close to the surface of the rotating shaft 30.
  • the height of the at least one stopper on the rotating shaft 30 is between 3.0 and 20.0 mm.
  • At least one depression is provided on the stopper, and the depth of the depression is 1.00 to 3.00 mm.
  • the at least one stopper provided on the inner surface of the reaction tube and the at least one stopper provided on the rotating shaft 30 are staggered with each other, so that the rotational movement between the reaction tube and the rotating shaft 30 is not affected.
  • the height of the at least one stopper provided on the inner surface of the reaction tube can be flexibly set according to the size of the reaction tube and the rotating shaft 30, but the height of the stopper cannot be too high, at least it cannot contact the surface of the rotating shaft 30, so as not to affect the rotation of the rotating shaft 30.
  • the height of at least one stopper provided on the rotating shaft 30 can be flexibly set according to the size of the reaction tube and the rotating shaft 30 , but the height of the stopper cannot be too high, at least it cannot contact the inner surface of the reaction tube to avoid affecting the rotation of the rotating shaft 30 .
  • At least two baffles are arranged on the inner surface of the reaction tube, and at least two baffles are spaced apart from each other in the radial direction and arranged on the inner surface of the reaction tube.
  • Each baffle includes at least two depressions, and the at least two depressions are evenly arranged on the baffle.
  • 6 baffles are arranged on the inner surface of the reaction tube, and the 6 baffles are spaced apart from each other in the radial direction and arranged on the inner surface of the reaction tube.
  • Each baffle includes 8 depressions, and the 8 depressions are evenly arranged on the same baffle.
  • the depth of the depression is 1.0 to 3.0 mm
  • the width is 1.0 to 3.0 mm
  • the depression is in the shape of a cuboid
  • the length is between 2.0 and 10.0 mm
  • the height of the baffle is between 3.0 and 20.0 mm
  • the interval between one baffle and another baffle is 4.0 to 22.0 mm.
  • the number of baffles, the number of depressions in each baffle, the shape of each depression, and the size of each depression do not need to be set strictly according to the above embodiments.
  • the general principle is to disturb the reactant flow flowing through the reaction tube by the baffles and depressions on the inner surface of the reaction tube to avoid back mixing and enhance the mixing effect and mass transfer effect of the reactants.
  • baffles it is better to set more than 3 groups of baffles on the inner surface of the reaction tube. Generally, 3-20 baffles are set. If the reaction tube is long, more baffles can be set, such as 30, 50, or even 100. 6-12 depressions are set on each baffle, but more depressions can also be set according to the circumference of the shaft and the tube. The interval between each depression is 2.0-5.0 mm, which can achieve better results.
  • At least two baffles are provided on the surface of the rotating shaft 30, and the at least two baffles are spaced apart from each other in the radial direction and are provided on the surface of the rotating shaft 30.
  • Each baffle includes at least two depressions, and the at least two depressions are evenly provided on the surface of the rotating shaft 30 at the same radial position.
  • six baffles are provided on the surface of the rotating shaft 30, and the six baffles are spaced apart from each other in the radial direction and are provided on the surface of the rotating shaft 30.
  • Each baffle includes eight depressions, and the eight depressions are evenly provided on the same baffle.
  • the width of the depression is 1.0 to 3.0 mm
  • the depth of the depression is 1.0 to 3.0 mm
  • the depression is in the shape of a cuboid
  • the length is between 2.0 and 10.0 mm
  • the height of the baffle is between 3.0 and 20.0 mm
  • the interval between one baffle and another baffle is 4.0 to 22.0 mm.
  • the number of baffles, the number of depressions in each baffle, the shape of each depression, and the size of each depression do not need to be set strictly according to the above embodiments.
  • the general principle is to disturb the reactant flow flowing through the reaction tube 20 by the baffles and depressions on the surface of the rotating shaft 30 to avoid back mixing and enhance the mixing effect and mass transfer effect of the reactants.
  • baffles According to the experience of the inventors of this application, it is better to set more than 3 baffles on the inner surface of the rotating shaft 30, and generally 3-20 baffles are set. If the reaction tube is long, more baffles can be set, such as 30, 50, or even 100. Each baffle is set with 6-12 depressions, which can achieve better results.
  • the first heat exchanger 10 and the second heat exchanger 11 are assembled into a cylinder, the inner diameter of which is the same as the outer diameter of the reaction tube, and the length of which is equal to the length of the reaction tube.
  • the first heat exchanger 10 and the second heat exchanger 11 are tightly fitted on the outside of the reaction tube and fixed on the reaction tube by the first outer ring flange clamp 50, the second outer ring flange clamp 51, the third outer ring flange clamp 52, and the fourth outer ring flange clamp 53.
  • Sealing gaskets are provided at the places where the first heat exchanger 10 and the second heat exchanger 11 are fitted to each other, and at the places where the first heat exchanger 10 and the second heat exchanger 11 are fitted to the reaction tube at both ends.
  • the inner walls of the first heat exchanger 10 and the second heat exchanger 11 have grooved passages, the passages are 5.0 to 20.0 mm wide and 2.0 to 20.0 mm deep.
  • the first flange cover 40 and the second flange cover 41 are installed at both ends of the reaction tube and seal the reaction tube.
  • FIG7 is a structural diagram of the flange cover of the dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention.
  • four inlet/outlet ports are arranged on the first flange cover 40: the first inlet/outlet port 400, the second inlet/outlet port 401, the third inlet/outlet port 402, and the fourth inlet/outlet port 403, and these four inlet/outlet ports can also be used as temperature detection ports.
  • inlet/outlet ports are arranged on the second flange cover 41: the fifth inlet/outlet port 410, the sixth inlet/outlet port 411, the seventh inlet/outlet port 412, and the eighth inlet/outlet port 413.
  • the drive device 70 is configured to be able to drive the rotating shaft 30 to rotate relative to the reaction tube.
  • the output shaft of the drive device 70 is coaxially connected to the rotating shaft 30 through a coupling 60, so that when the drive device 70 rotates, it can drive the rotating shaft 30 to rotate together, so that the baffles on the inner surface of the reaction tube (staggered and adjacent to each other) and the baffles on the surface of the rotating shaft 30 also move relative to each other, and the reactant fluid flowing through the inner cavity of the reaction tube is subjected to the lateral shear force of the rotating shaft 30, which will passively form turbulence, and enter the convex and concave parts of the adjacent reaction tube surface baffles through the tiny gap between the top of the baffle on the surface of the rotating shaft 30 and the reaction tube, and is further blocked, diverted, and mixed again.
  • the above reactors were integrated, and the specific reactor parameters were as follows: 1) The diameter of the rotating shaft 30 was 15.0 mm, the height of the baffle was 4.0 mm, the width was 4.0 mm, the width of the teeth on the baffle was 2.0 mm, the number of depressions on each baffle was 8, the depth of each depression was 1.0 mm, there were 6 baffles in total, the length of each repeating unit (including a baffle and an adjacent cavity) was 12.0 mm, the length of the shaft 30 was 90 mm, and the rotation speed was 200 rpm; 2) The wall thickness of the reaction tube 20 was 4.0 mm, the height of the baffle was 4.0 mm, the width was 4.0 mm, the width of the teeth on the baffle was 2.0 mm, the number of depressions on each baffle was 8 , each depression has a depth of 1.0 mm, there are 6 sets of baffles in total, the length of each repeating unit (including a baffle and an adjacent cavity) is 12.0 mm, the outer diameter of the
  • the water emulsion is prepared by using three fluid feeds of vegetable oil (fluid one), emulsifier (fluid two) and water (fluid three).
  • the feed rate of vegetable oil is 10mL/min
  • the emulsifier is 15mL/min
  • the water feed rate is 30mL/min.
  • the three fluids are fed from the feed port at the same end at 20-25°C. After mixing by the shear force of the rotating shaft, a water emulsion is obtained. Analysis and detection show that the oil droplet size is about 0.9 ⁇ m.
  • the heat exchange capacity was verified. 60°C water was used as the only fluid to be injected into the reactor from the feed port and out of the other end of the discharge port.
  • the fluid flow rate was 50mL/min
  • the heat exchange jacket temperature was set to 30°C
  • the heat transfer oil flow rate in the heat exchanger was 35L/min.
  • the temperature information of the hot water fluid entering and leaving the reactor was monitored. After the overall working conditions were stabilized, after the 60°C hot water passed through the reactor, the actual measured fluid temperature at the discharge port was 31°C, which was +1.0°C lower than the temperature of the heat exchanger jacket, and the error range was less than 4.0%.
  • the interior of the reaction tube 20 is designed to be smooth without continuous protrusions, and the remaining components, such as heat exchangers 10 and 11, shaft 30, flange covers 40 and 41, and flange clamps 50-53, are the same as those in Example 1.
  • This scheme is used to test the mixing effect, and three fluids, vegetable oil (fluid one), emulsifier (fluid two) and water (fluid three), are fed at 20-25°C to prepare an aqueous emulsion.
  • the feed rate of vegetable oil is 10mL/min
  • the emulsifier is 15mL/min
  • the feed rate of water is 30mL/min.
  • the three fluids are fed from the feed port at the same end, and the aqueous emulsion is obtained after mixing by the shear force of the shaft.
  • the oil droplet size is about 2.5 ⁇ m after analysis.
  • 60°C water is used as the only fluid to be injected into the reactor from the feed port and out of the other end of the discharge port.
  • the fluid flow rate is 50mL/min
  • the heat exchange jacket temperature is set to 30°C
  • the heat transfer oil flow rate in the heat exchanger is 35L/min. Monitor the temperature information of the hot water fluid entering and leaving the reactor. After the overall working conditions are stable, after the 60°C hot water passes through the reactor, the actual measured fluid temperature at the discharge port is 35°C, which is +5.0°C different from the heat exchanger jacket temperature, and the error range is about 17%.
  • the grooves inside the heat exchanger are removed, and the inner surface of the heat exchanger is a smooth structure.
  • the remaining components, such as the reaction tube 20, the rotating shaft 30, the flange covers 40 and 41, and the flange clamps 50-53 are the same as those in Example 1.
  • 60°C water is used as the only fluid to be injected into the reactor from the feed port and out of the other end of the discharge port.
  • the fluid flow rate is 50mL/min
  • the heat exchange jacket temperature is set to 30°C
  • the heat transfer oil flow rate in the heat exchanger is 35L/min. Monitor the temperature information of the hot water fluid when it enters and exits the reactor. After the overall working conditions are stable, after the 60°C hot water passes through the reactor, the actual measured fluid temperature at the discharge port is 31.5°C, which is +1.5°C different from the heat exchanger jacket temperature, and the error range is less than 5.0%.
  • Example 1 The dynamic microchannel tubular continuous reactor provided by the embodiment of the present invention has a better oil-water mixing emulsification effect than that of the ordinary tubular reactor. Under the test conditions, the particle size of the emulsified oil droplets is reduced by 178% (0.9 ⁇ m vs. 2.5 ⁇ m), and the overall emulsification is more sufficient; 2) The concave-convex design of the reaction tube and the grooved reflux flow design of the heat exchanger increase the heat exchange area inside the reactor, and the overall heat exchange capacity of the reactor is improved. Under the test conditions, the fluid inlet temperature of Example 1 is closest to the temperature of the heat exchanger oil, and the temperature control is more precise.

Abstract

A dynamic combined micro-channel continuous flow reactor, comprising a reaction tube, a rotating shaft (30), a first heat exchanger (10), a second heat exchanger (11), a coupler (60) and a driving device (70), wherein the reaction tube comprises a first-half reaction tube (20) and a second-half reaction tube (21); the inner diameter of the reaction tube is greater than the outer diameter of the rotating shaft (30), and the rotating shaft (30) is coaxially arranged inside the reaction tube; the driving device (70) is configured to be capable of driving the rotating shaft (30) to rotate relative to the reaction tube; and the first-half reaction tube (20) and the second-half reaction tube (21) are two half cylinders of the same shape and size, and are assembled together to form the reaction tube having a cylindrical space therein. A reactor pipeline has the same size as a common tubular reactor, and micro-reaction channels are formed in the reaction tube by means of baffle structures, which have recesses, on the tube inner wall and the rotating shaft (30), such that the mass and heat transfer efficiency of the tubular reactor is improved.

Description

一种动态混合微通道连续流反应器A dynamic mixing microchannel continuous flow reactor 技术领域Technical Field
本发明涉及连续流反应装置领域,特别涉及一种动态混合微通道连续流反应器。The invention relates to the field of continuous flow reaction devices, in particular to a dynamic mixing microchannel continuous flow reactor.
背景技术Background technique
常见的微通道反应器为平面结构,属于静态混合器,虽然传质换热效果好,但对于反应器的固含量的承载能力较弱(一般必须小于10%的固载量,且固体粒径小于0.5mm)。对于固含量承载能力相对较好的管式反应器,其传质效果较差,且管径越大传质传热效果越差,放大效应越明显,从而导致生产效率较低。即使将管式反应器设计成动态转轴混合的形式,增加湍流,增强传质效果,其传质传热效果仍比传统的微通道连续流反应器相差甚远。从而使得常规连续流反应器的特异性较强,普适性较弱,需要针对不同工艺定制生产设备,相关的投入较高。故产业界急需一类工艺普适性强,可以快速组装的连续流反应器。Common microchannel reactors are planar structures and belong to static mixers. Although they have good mass transfer and heat exchange effects, their solid content carrying capacity for the reactor is relatively weak (generally, the solid loading must be less than 10%, and the solid particle size must be less than 0.5 mm). For tubular reactors with relatively good solid content carrying capacity, their mass transfer effect is poor, and the larger the tube diameter, the worse the mass transfer and heat transfer effect, and the more obvious the amplification effect, resulting in low production efficiency. Even if the tubular reactor is designed in the form of dynamic rotating shaft mixing, turbulence is increased, and the mass transfer effect is enhanced, its mass transfer and heat transfer effect is still far from that of the traditional microchannel continuous flow reactor. As a result, the conventional continuous flow reactor has strong specificity and weak universality, and production equipment needs to be customized for different processes, and the related investment is high. Therefore, the industry is in urgent need of a type of continuous flow reactor with strong process universality and can be assembled quickly.
发明内容Summary of the invention
针对现有技术存在的上述问题,本发明的目的在于提供一种动态混合微通道连续流反应器,旨在解决微通道固体承载量较低、容易堵塞通道,以及常见管式反应器混合效果不佳、换热能力弱等缺点,从而实现一种反应器对多种反应类型的覆盖,增加设备使用率,提升生产效率,降低生产成本。为实现以上目的,本发明通过以下技术方案予以实现:In view of the above problems existing in the prior art, the purpose of the present invention is to provide a dynamic mixing microchannel continuous flow reactor, aiming to solve the shortcomings of low solid loading capacity of microchannels, easy channel clogging, poor mixing effect and weak heat exchange capacity of common tubular reactors, so as to achieve one reactor to cover multiple reaction types, increase equipment utilization, improve production efficiency and reduce production costs. To achieve the above purpose, the present invention is implemented through the following technical solutions:
将反应管内曲面与转轴设计为凹凸不平的连续多级结构,反应管内壁与转轴彼此嵌套,组成微小反应通道,同时通过转轴提供横向剪切力,作为动态混合的动力。反应管设计成二合一的分体式结构,一方面拆装检修方便,另一方面可以在反应管内表面和转轴表面设计高度更高的凸起,这样可以形成尺寸更小的微通道,进一步加强了传质效果。The inner curved surface of the reaction tube and the rotating shaft are designed as a continuous multi-level structure with uneven surfaces. The inner wall of the reaction tube and the rotating shaft are nested with each other to form a tiny reaction channel. At the same time, the rotating shaft provides lateral shear force as the driving force for dynamic mixing. The reaction tube is designed as a two-in-one split structure. On the one hand, it is easy to disassemble and repair. On the other hand, higher protrusions can be designed on the inner surface of the reaction tube and the surface of the rotating shaft, so that a smaller microchannel can be formed, further enhancing the mass transfer effect.
本发明优选实施方案:Preferred embodiments of the present invention:
1)将转轴设计为分列式的高低凸起多齿状,高凸起高度3.0~20.0mm,凹陷部分高度为1.0~3.0mm,整体凹陷部分与反应管凸起处嵌套,可供流体经过,从侧面看为多齿结构;1) The rotating shaft is designed to be a multi-tooth structure with high and low protrusions, the height of the high protrusion is 3.0-20.0 mm, the height of the concave part is 1.0-3.0 mm, and the overall concave part is nested with the protrusion of the reaction tube to allow fluid to pass through, and it is a multi-tooth structure when viewed from the side;
2)反应管主体为一个反应物容器腔,为分体式结构,可一分为二,贴合处有密封垫片,通过容器腔内壁设计为分列式的连续流多级结构,凸出部分作为挡台,挡台高度介于 3.0~20.0mm,同时挡台面上也有规则凹陷结构,此处凹陷结构深度为1.00~3.00mm,挡台与挡台之间有整体凹陷部分与转轴凸起处嵌套,可供流体经过,从侧面看为内多齿结构;2) The main body of the reaction tube is a reactant container cavity, which is a split structure and can be divided into two. There is a sealing gasket at the joint. The inner wall of the container cavity is designed as a split-type continuous flow multi-stage structure. The protruding part is used as a baffle. The height of the baffle is between 3.0 and 20.0 mm. At the same time, there is also a regular concave structure on the baffle surface. The depth of the concave structure here is 1.00 to 3.00 mm. There is an integral concave part between the baffles and the protrusion of the rotating shaft nested, which can allow fluid to pass through. From the side, it is an internal multi-tooth structure;
3)转轴与反应管主体嵌套结构中,转轴凸起顶部与反应管凹陷整体底部的距离介于1.0~3.0mm,反应管凸起顶部与转轴整体凹陷底部的距离介于1.0~3.0mm;3) In the nested structure of the rotating shaft and the reaction tube body, the distance between the top of the rotating shaft protrusion and the bottom of the overall depression of the reaction tube is between 1.0 and 3.0 mm, and the distance between the top of the reaction tube protrusion and the bottom of the overall depression of the rotating shaft is between 1.0 and 3.0 mm;
4)在反应管外部采用可拆卸、分体式的折返流通道类型夹套换热器,可一分为二,贴合处有密封垫圈,且通过固定螺栓与反应管重叠进行整合,换热器内部刻槽与反应管外壁紧密贴合,形成换热通路;4) A detachable, split-type return flow channel type jacket heat exchanger is used outside the reaction tube, which can be divided into two parts, with a sealing gasket at the joint, and is integrated with the reaction tube by overlapping with fixing bolts. The groove inside the heat exchanger is tightly fitted with the outer wall of the reaction tube to form a heat exchange passage;
5)反应管两端由快拆法兰组成,用于整体密封,以及承载机封,固定转轴;5) Both ends of the reaction tube are composed of quick-release flanges, which are used for overall sealing, as well as bearing mechanical seals and fixing the rotating shaft;
6)驱动装置,采用伺服电机或者气动马达等带动转轴进行转动,并可实现多级变速调整。6) The driving device adopts a servo motor or a pneumatic motor to drive the rotating shaft to rotate, and can realize multi-level speed adjustment.
本发明的有益效果在于,采用本发明采用独特的结构设计,即:一方面,本发明采用的反应器管道尺寸是通常管式反应器的尺寸,而在内部通过管内壁的以及转轴上的具有凹陷的挡台结构,在反应管内形成了微反应通道,从而极大地提高了管式反应器的传质传热效率,同时具备了微通道连续流反应器传质效率高与管式反应器通量大的优点,但又避免了微通道反应器固体承载量较低、以及常规管式反应器传质传热较差的缺点。反应管设计成分体式结构,方便拆装,也由此可以将管内壁的具有凹陷的挡台结构以及转轴上的凸起结构设计成较大尺寸,从而能够形成尺寸更小的微通道,避免返混现象,进一步增强了传质效果。The beneficial effect of the present invention lies in that the present invention adopts a unique structural design, namely: on the one hand, the reactor pipe size adopted by the present invention is the size of a common tubular reactor, and a micro-reaction channel is formed in the reaction tube through the inner wall of the tube and the concave baffle structure on the rotating shaft, thereby greatly improving the mass transfer and heat transfer efficiency of the tubular reactor, and at the same time having the advantages of high mass transfer efficiency of the microchannel continuous flow reactor and large flux of the tubular reactor, but avoiding the disadvantages of low solid carrying capacity of the microchannel reactor and poor mass transfer and heat transfer of the conventional tubular reactor. The reaction tube is designed as a split structure, which is convenient for disassembly and assembly, and thus the concave baffle structure on the inner wall of the tube and the convex structure on the rotating shaft can be designed to be larger in size, so that a smaller microchannel can be formed, back-mixing phenomenon can be avoided, and the mass transfer effect is further enhanced.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1是本发明实施例提供的动态混合微通道连续流反应器爆炸附图。FIG1 is an exploded view of a dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention.
图2是本发明实施例提供的动态混合微通道连续流反应器整体结构示意图。FIG2 is a schematic diagram of the overall structure of a dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention.
图3是本发明实施例提供的动态混合微通道连续流反应器整体结构的纵截面图。3 is a longitudinal cross-sectional view of the overall structure of a dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention.
图4是本发明实施例提供的动态混合微通道连续流反应器中换热器结构示意图。FIG. 4 is a schematic diagram of the structure of a heat exchanger in a dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention.
图5是本发明实施例提供动态混合微通道连续流反应器中反应管结构示意图。FIG5 is a schematic diagram of the reaction tube structure in a dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention.
图6是本发明实施例提供的动态混合微通道连续流反应器中转轴结构示意图。FIG6 is a schematic diagram of the structure of the rotating shaft in the dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention.
图7是本发明实施例提供的动态混合微通道连续流反应器中法兰盖结构示意图。FIG. 7 is a schematic diagram of the flange cover structure in a dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention.
Figure PCTCN2022121198-appb-000001
Figure PCTCN2022121198-appb-000001
Figure PCTCN2022121198-appb-000002
Figure PCTCN2022121198-appb-000002
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚明白,以下结合具体实施例,并参照附图,对本发明进一步详细说明。但本领域技术人员知晓,本发明并不局限于附图和以下实施例。To make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings. However, those skilled in the art will appreciate that the present invention is not limited to the accompanying drawings and the following embodiments.
在发明的描述中,需要说明的是,对于方位词,如术语“长度”、“宽度”、“上”、“下”、“远”、“近”等所指示的方位或位置关系是基于附图所示的方位或位置关系,仅是为了便于叙述本发明和简化描述,而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定方位构造和操作,不能理解为限制本发明的具体保护范围。此外,术语“第一”、“第二”仅用于描述目的,用以区别技术特征,不具有实质含义,不能理解为指示或暗示相对重要性或隐含指明技术特征的数量。In the description of the invention, it should be noted that the orientation or positional relationship indicated by the terms "length", "width", "upper", "lower", "far", "near", etc. is based on the orientation or positional relationship shown in the drawings, which is only for the convenience of describing the invention and simplifying the description, and does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and cannot be understood as limiting the specific protection scope of the invention. In addition, the terms "first" and "second" are only used for descriptive purposes to distinguish technical features, and do not have substantial meanings, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features.
实施例1Example 1
本发明的实施例提出一种动态混合微通道连续流反应器。参照图1和2,所述动态混合微通道连续流反应器包括反应管、转轴30、第一换热器10和第二换热器11、联轴器60和驱动装置70。反应管包括第一半反应管20和第二半反应管21,反应管的内径大于转轴30的外径,转轴30以同轴的方式设置在反应管20内部,驱动装置70配置为能够驱动转轴30与反应管相对做旋转运动。第一半反应管20和第二半反应管21为两个形状、尺寸相同的半圆柱,两者拼合在一起形成一个内部有圆柱形空间的反应管(参见图4)。第一半反应管20和第二半反应管21通过横向部位的螺栓进行整体固定,且两者径向贴合面设置有PTFE密封垫片。The embodiment of the present invention proposes a dynamic mixing microchannel continuous flow reactor. Referring to Figures 1 and 2, the dynamic mixing microchannel continuous flow reactor includes a reaction tube, a rotating shaft 30, a first heat exchanger 10 and a second heat exchanger 11, a coupling 60 and a driving device 70. The reaction tube includes a first half reaction tube 20 and a second half reaction tube 21, the inner diameter of the reaction tube is greater than the outer diameter of the rotating shaft 30, the rotating shaft 30 is coaxially arranged inside the reaction tube 20, and the driving device 70 is configured to be able to drive the rotating shaft 30 to rotate relative to the reaction tube. The first half reaction tube 20 and the second half reaction tube 21 are two semi-cylinders of the same shape and size, and the two are assembled together to form a reaction tube with a cylindrical space inside (see Figure 4). The first half reaction tube 20 and the second half reaction tube 21 are fixed as a whole by bolts in the transverse position, and the radial fitting surfaces of the two are provided with PTFE sealing gaskets.
如图1、图5所示,由第一半反应管20和第二半反应管21拼合后组成的反应管内表面设置至少一个挡台,挡台呈圆周状紧贴反应管内表面,反应管内表面的至少一个挡台高度介于3.0~20.0mm,在挡台上设置至少一个凹陷,凹陷的深度为1.00~3.00mm。如图6所示, 转轴30上设置至少一个挡台,挡台呈圆周状紧贴转轴30的表面,转轴30上的至少一个挡台高度介于3.0~20.0mm,在挡台上设置至少一个凹陷,凹陷的深度为1.00~3.00mm。反应管内表面设置的至少一个挡台与转轴30上设置的至少一个挡台相互错开,使得反应管与转轴30之间的旋转运动不受影响。反应管内表面设置的至少一个挡台的高度可以根据反应管、转轴30的尺寸灵活设置,但挡台的高度不能过高,至少不能与转轴30表面接触,以免影响转轴30的转动。同样的,转轴30上设置的至少一个挡台的高度可以根据反应管、转轴30的尺寸灵活设置,但挡台的高度不能过高,至少不能与反应管的内表面接触,以免影响转轴30的转动。As shown in FIG. 1 and FIG. 5 , at least one stopper is provided on the inner surface of the reaction tube formed by the first half reaction tube 20 and the second half reaction tube 21. The stopper is in a circular shape and close to the inner surface of the reaction tube. The height of the at least one stopper on the inner surface of the reaction tube is between 3.0 and 20.0 mm. At least one depression is provided on the stopper, and the depth of the depression is 1.00 to 3.00 mm. As shown in FIG. 6 , at least one stopper is provided on the rotating shaft 30. The stopper is in a circular shape and close to the surface of the rotating shaft 30. The height of the at least one stopper on the rotating shaft 30 is between 3.0 and 20.0 mm. At least one depression is provided on the stopper, and the depth of the depression is 1.00 to 3.00 mm. The at least one stopper provided on the inner surface of the reaction tube and the at least one stopper provided on the rotating shaft 30 are staggered with each other, so that the rotational movement between the reaction tube and the rotating shaft 30 is not affected. The height of the at least one stopper provided on the inner surface of the reaction tube can be flexibly set according to the size of the reaction tube and the rotating shaft 30, but the height of the stopper cannot be too high, at least it cannot contact the surface of the rotating shaft 30, so as not to affect the rotation of the rotating shaft 30. Similarly, the height of at least one stopper provided on the rotating shaft 30 can be flexibly set according to the size of the reaction tube and the rotating shaft 30 , but the height of the stopper cannot be too high, at least it cannot contact the inner surface of the reaction tube to avoid affecting the rotation of the rotating shaft 30 .
根据本发明的一种实施方式,例如,反应管内表面设置至少两个挡台,至少两个挡台沿径向彼此间隔开,设置在反应管内表面。每一个挡台包括至少两个凹陷,上述至少两个凹陷均匀设置在挡台上。如图5所示,反应管内表面设置6个挡台,6个挡台沿径向彼此间隔开,设置在反应管内表面。每一个挡台包括8个凹陷,上述8个凹陷均匀设置在同一个挡台上。同一个挡台内部,凹陷深度为1.0~3.0mm,宽度为1.0~3.0mm,凹陷呈长方体形,长度介于2.0~10.0mm,挡台高度介于3.0~20.0mm,一个挡台与另个挡台之间的间隔为4.0~22.0mm。一共设置几个挡台、每个挡台中设置几个凹陷、每一个凹陷设置成什么形状、其尺寸多大,实际上并不需要严格按照上述实施例中的情形来设置,总体的原则是要通过这些反应管内表面的挡台及凹陷来扰乱流经反应管内部的反应物流,以避免返混,并增强反应物的混合效果及传质效果。根据本申请发明人的经验,反应管内表面的挡台设置3组以上效果较好,一般设置3-20个,如果反应管长度较长,也可以设置更多个,例如30个、50个、甚至100个。每一个挡台上设置6-12个凹陷,但也可以根据轴与管的周长设置更多的凹陷,每个凹陷之间间隔2.0~5.0mm,能够取得比较好的效果。According to one embodiment of the present invention, for example, at least two baffles are arranged on the inner surface of the reaction tube, and at least two baffles are spaced apart from each other in the radial direction and arranged on the inner surface of the reaction tube. Each baffle includes at least two depressions, and the at least two depressions are evenly arranged on the baffle. As shown in FIG5 , 6 baffles are arranged on the inner surface of the reaction tube, and the 6 baffles are spaced apart from each other in the radial direction and arranged on the inner surface of the reaction tube. Each baffle includes 8 depressions, and the 8 depressions are evenly arranged on the same baffle. Inside the same baffle, the depth of the depression is 1.0 to 3.0 mm, the width is 1.0 to 3.0 mm, the depression is in the shape of a cuboid, the length is between 2.0 and 10.0 mm, the height of the baffle is between 3.0 and 20.0 mm, and the interval between one baffle and another baffle is 4.0 to 22.0 mm. The number of baffles, the number of depressions in each baffle, the shape of each depression, and the size of each depression do not need to be set strictly according to the above embodiments. The general principle is to disturb the reactant flow flowing through the reaction tube by the baffles and depressions on the inner surface of the reaction tube to avoid back mixing and enhance the mixing effect and mass transfer effect of the reactants. According to the experience of the inventors of this application, it is better to set more than 3 groups of baffles on the inner surface of the reaction tube. Generally, 3-20 baffles are set. If the reaction tube is long, more baffles can be set, such as 30, 50, or even 100. 6-12 depressions are set on each baffle, but more depressions can also be set according to the circumference of the shaft and the tube. The interval between each depression is 2.0-5.0 mm, which can achieve better results.
根据本发明的一种实施方式,例如,转轴30的表面设置至少两个挡台,至少两个挡台沿径向彼此间隔开,设置在转轴30表面。每一个挡台包括至少两个凹陷,上述至少两个凹陷均匀设置在转轴30同一径向位置的表面。如图6所示,转轴30表面设置6个挡台,6个挡台沿径向彼此间隔开,设置在转轴30表面。每一个挡台包括8个凹陷,上述8个凹陷均匀设置在同一挡台上。同一个挡台内部,凹陷宽度1.0~3.0mm,凹陷深度为1.0~3.0mm,凹陷呈长方体形,长度介于2.0~10.0mm,挡台高度介于3.0~20.0mm,一个挡台与另一个挡台之间的间隔为4.0~22.0mm。一共设置几个挡台、每一个挡台中设置几个凹陷、每一个凹陷设置成什么形状、其尺寸多大,实际上并不需要严格按照上述实施例中的情形来设置,总体的原则是要通过这些转轴30表面的挡台及凹陷来扰乱流经反应管20内部的反应物流,以避免返混, 并增强反应物的混合效果及传质效果。根据本申请发明人的经验,转轴30内表面的挡台设置3个以上效果较好,一般设置3-20个,如果反应管长度较长,也可以设置更多个,例如30个、50个、甚至100个。每一个挡台设置6-12个凹陷,能够取得比较好的效果。According to one embodiment of the present invention, for example, at least two baffles are provided on the surface of the rotating shaft 30, and the at least two baffles are spaced apart from each other in the radial direction and are provided on the surface of the rotating shaft 30. Each baffle includes at least two depressions, and the at least two depressions are evenly provided on the surface of the rotating shaft 30 at the same radial position. As shown in FIG6 , six baffles are provided on the surface of the rotating shaft 30, and the six baffles are spaced apart from each other in the radial direction and are provided on the surface of the rotating shaft 30. Each baffle includes eight depressions, and the eight depressions are evenly provided on the same baffle. Inside the same baffle, the width of the depression is 1.0 to 3.0 mm, the depth of the depression is 1.0 to 3.0 mm, the depression is in the shape of a cuboid, the length is between 2.0 and 10.0 mm, the height of the baffle is between 3.0 and 20.0 mm, and the interval between one baffle and another baffle is 4.0 to 22.0 mm. The number of baffles, the number of depressions in each baffle, the shape of each depression, and the size of each depression do not need to be set strictly according to the above embodiments. The general principle is to disturb the reactant flow flowing through the reaction tube 20 by the baffles and depressions on the surface of the rotating shaft 30 to avoid back mixing and enhance the mixing effect and mass transfer effect of the reactants. According to the experience of the inventors of this application, it is better to set more than 3 baffles on the inner surface of the rotating shaft 30, and generally 3-20 baffles are set. If the reaction tube is long, more baffles can be set, such as 30, 50, or even 100. Each baffle is set with 6-12 depressions, which can achieve better results.
参照图5和图6,由于反应管内表面和转轴30表面都设置了挡台,并且,反应管内表面设置的6个挡台与转轴30表面设置的6个挡台彼此错开,以及不论是反应管内表面的挡台还是转轴30表面的挡台,每一个挡台都包括8个凹陷(从而也就形成8个凸起),且均匀分布,于是转轴30可以旋转到一个位置,使得转轴30上的任一个凸起都位于反应管内表面相邻两个凸起之间。这样,流经反应管内表面相邻两个凸起之间的间隙的反应液遇到转轴30上凸起的阻挡而改变流向,这进一步增强了反应物的混合效果及传质效果。5 and 6, since both the inner surface of the reaction tube and the surface of the rotating shaft 30 are provided with baffles, and the 6 baffles provided on the inner surface of the reaction tube and the 6 baffles provided on the surface of the rotating shaft 30 are staggered with each other, and each baffle, whether on the inner surface of the reaction tube or on the surface of the rotating shaft 30, includes 8 depressions (thus forming 8 protrusions), and is evenly distributed, the rotating shaft 30 can be rotated to a position so that any protrusion on the rotating shaft 30 is located between two adjacent protrusions on the inner surface of the reaction tube. In this way, the reaction liquid flowing through the gap between two adjacent protrusions on the inner surface of the reaction tube encounters the obstruction of the protrusion on the rotating shaft 30 and changes its flow direction, which further enhances the mixing effect and mass transfer effect of the reactants.
如图1、图2所示,第一换热器10和第二换热器11拼合后为一圆筒,该圆筒内径与反应管的外径相同,且该圆筒长度与反应管长度相等,第一换热器10和第二换热器11紧密贴合在反应管外侧,由第一外圈法兰夹50、第二外圈法兰夹51、第三外圈法兰夹52、第四外圈法兰夹53固定在反应管上。在第一换热器10和第二换热器11相互贴合之处,以及在第一换热器10和第二换热器11两端与反应管贴合之处设置密封垫。第一换热器10和第二换热器11内壁具有刻槽型通路,通路宽5.0~20.0mm,深2.0~20.0mm。第一换热器10和第二换热器11两端分别有一个进/出液口,供导热流体进/出。第一法兰盖40和第二法兰盖41安装在反应管两端并密封反应管。如图2所示,转轴30一端穿过第一法兰盖40的中心孔,另一端穿过第二法兰盖41的中心孔,通过连轴器60与驱动装置70的动力输出轴相连接。图7是本发明实施例提供的动态混合微通道连续流反应器的法兰盖结构图。如图7所示,在第一法兰盖40上设置四个进/出料口:第一进/出料口400,第二进/出料口401,第三进/出料口402,第四进/出料口403,这四个进/出料口同时也可以作为探温口。在第二法兰盖41上设置四个进/出料口:第五进/出料口410,第六进/出料口411,第七进/出料口412、第八进/出料口413。As shown in FIG. 1 and FIG. 2, the first heat exchanger 10 and the second heat exchanger 11 are assembled into a cylinder, the inner diameter of which is the same as the outer diameter of the reaction tube, and the length of which is equal to the length of the reaction tube. The first heat exchanger 10 and the second heat exchanger 11 are tightly fitted on the outside of the reaction tube and fixed on the reaction tube by the first outer ring flange clamp 50, the second outer ring flange clamp 51, the third outer ring flange clamp 52, and the fourth outer ring flange clamp 53. Sealing gaskets are provided at the places where the first heat exchanger 10 and the second heat exchanger 11 are fitted to each other, and at the places where the first heat exchanger 10 and the second heat exchanger 11 are fitted to the reaction tube at both ends. The inner walls of the first heat exchanger 10 and the second heat exchanger 11 have grooved passages, the passages are 5.0 to 20.0 mm wide and 2.0 to 20.0 mm deep. There is an inlet/outlet at each end of the first heat exchanger 10 and the second heat exchanger 11 for the heat transfer fluid to enter/exit. The first flange cover 40 and the second flange cover 41 are installed at both ends of the reaction tube and seal the reaction tube. As shown in FIG2 , one end of the rotating shaft 30 passes through the center hole of the first flange cover 40, and the other end passes through the center hole of the second flange cover 41, and is connected to the power output shaft of the driving device 70 through the coupling 60. FIG7 is a structural diagram of the flange cover of the dynamic mixing microchannel continuous flow reactor provided in an embodiment of the present invention. As shown in FIG7 , four inlet/outlet ports are arranged on the first flange cover 40: the first inlet/outlet port 400, the second inlet/outlet port 401, the third inlet/outlet port 402, and the fourth inlet/outlet port 403, and these four inlet/outlet ports can also be used as temperature detection ports. Four inlet/outlet ports are arranged on the second flange cover 41: the fifth inlet/outlet port 410, the sixth inlet/outlet port 411, the seventh inlet/outlet port 412, and the eighth inlet/outlet port 413.
驱动装置70配置为能够驱动转轴30与反应管相对做旋转运动。根据本发明的一种实施方式,如图1、图2所示,驱动装置70的输出轴通过联轴器60与转轴30同轴连接,于是驱动装置70旋转时能够带动转轴30一起旋转,于是(彼此相互错开、彼此相邻的)反应管内表面的挡台与转轴30表面的挡台也发生相对运动,流经反应管内腔的反应物流体受到转轴30横向剪切的作用力,会被动地形成乱流,并通过转轴30表面挡台顶部与反应管之间的微小空隙进入相邻的反应管表面挡台的凸起、凹陷部分,并被进一步阻挡、分流,再次混合。以此类推,经过连续多次主动与被动混合之后,达到最佳的传质效果。同时得益于反应管内 壁的挡台,以及外部的第一换热器10和第二换热器11多级折返通道设计,极大地增加了换热比表面积,换热能力得到显著提升。The drive device 70 is configured to be able to drive the rotating shaft 30 to rotate relative to the reaction tube. According to one embodiment of the present invention, as shown in Figures 1 and 2, the output shaft of the drive device 70 is coaxially connected to the rotating shaft 30 through a coupling 60, so that when the drive device 70 rotates, it can drive the rotating shaft 30 to rotate together, so that the baffles on the inner surface of the reaction tube (staggered and adjacent to each other) and the baffles on the surface of the rotating shaft 30 also move relative to each other, and the reactant fluid flowing through the inner cavity of the reaction tube is subjected to the lateral shear force of the rotating shaft 30, which will passively form turbulence, and enter the convex and concave parts of the adjacent reaction tube surface baffles through the tiny gap between the top of the baffle on the surface of the rotating shaft 30 and the reaction tube, and is further blocked, diverted, and mixed again. By analogy, after continuous active and passive mixing for multiple times, the best mass transfer effect is achieved. At the same time, thanks to the baffles on the inner wall of the reaction tube, and the multi-stage return channel design of the first heat exchanger 10 and the second heat exchanger 11 outside, the heat exchange specific surface area is greatly increased, and the heat exchange capacity is significantly improved.
将上述反应器整合,具体的反应器参数如下:1)转轴30直径15.0mm,挡台高度为4.0mm,宽4.0mm,挡台上齿缝宽2.0mm,每个挡台凹陷数为8,每个凹陷深度为1.0mm,一共6个挡台,每个重复单元(包含一个挡台和一个相邻空腔)的长度为12.0mm,轴30长度为90mm,转动速率为200rpm;2)反应管20的管壁厚为4.0mm,挡台高度为4.0mm,宽4.0mm,挡台上齿缝宽2.0mm,每个挡台凹陷数为8,每个凹陷深度为1.0mm,一共6组挡台,每个重复单元(包含一个挡台和一个相邻空腔)的长度为12.0mm,反应管20的外直径为37.0mm,总长度为72mm;3)换热器10和11,通路宽度为5.0mm,肩宽3.0mm,深度为5.0mm,换热器整体壁厚为10mm,两片换热器长度均为72mm;4)转轴30与反应管20的材质为316L不锈钢,换热器的材质为铝合金;5)反应管20与转轴30螯合组装后,持液体积约19mL。优先进行传质效果验证,采用采用植物油(流体一)、乳化剂(流体二)和水(流体三)三种流体进料进行水乳剂的制备。植物油进料量为10mL/min,乳化剂为15mL/min,水进料量为30mL/min,三种流体在20~25℃条件下,从同一端的进料口进料,经过转轴的剪切力混合后得水乳剂,经分析检测油滴粒径约0.9μm。The above reactors were integrated, and the specific reactor parameters were as follows: 1) The diameter of the rotating shaft 30 was 15.0 mm, the height of the baffle was 4.0 mm, the width was 4.0 mm, the width of the teeth on the baffle was 2.0 mm, the number of depressions on each baffle was 8, the depth of each depression was 1.0 mm, there were 6 baffles in total, the length of each repeating unit (including a baffle and an adjacent cavity) was 12.0 mm, the length of the shaft 30 was 90 mm, and the rotation speed was 200 rpm; 2) The wall thickness of the reaction tube 20 was 4.0 mm, the height of the baffle was 4.0 mm, the width was 4.0 mm, the width of the teeth on the baffle was 2.0 mm, the number of depressions on each baffle was 8 , each depression has a depth of 1.0 mm, there are 6 sets of baffles in total, the length of each repeating unit (including a baffle and an adjacent cavity) is 12.0 mm, the outer diameter of the reaction tube 20 is 37.0 mm, and the total length is 72 mm; 3) The heat exchangers 10 and 11 have a passage width of 5.0 mm, a shoulder width of 3.0 mm, a depth of 5.0 mm, an overall wall thickness of the heat exchanger of 10 mm, and the length of the two heat exchangers is 72 mm; 4) The material of the shaft 30 and the reaction tube 20 is 316L stainless steel, and the material of the heat exchanger is aluminum alloy; 5) After the reaction tube 20 and the shaft 30 are chelated and assembled, the liquid holding volume is about 19 mL. The mass transfer effect is verified first, and the water emulsion is prepared by using three fluid feeds of vegetable oil (fluid one), emulsifier (fluid two) and water (fluid three). The feed rate of vegetable oil is 10mL/min, the emulsifier is 15mL/min, and the water feed rate is 30mL/min. The three fluids are fed from the feed port at the same end at 20-25°C. After mixing by the shear force of the rotating shaft, a water emulsion is obtained. Analysis and detection show that the oil droplet size is about 0.9μm.
再进行换热能力验证,采用60℃水作为唯一流体从进料口注入反应器中,另一端出料口出来,流体流速为50mL/min,换热夹套温度设定为30℃,换热器中导热油流速为35L/min。监控热水流体进入反应器和出反应器时的温度信息。待整体工况稳定之后,60℃热水经过反应器后,出料口实际测定的流体温度为31℃,与换热器夹套温度差距+1.0℃,误差范围小于4.0%。Then, the heat exchange capacity was verified. 60°C water was used as the only fluid to be injected into the reactor from the feed port and out of the other end of the discharge port. The fluid flow rate was 50mL/min, the heat exchange jacket temperature was set to 30°C, and the heat transfer oil flow rate in the heat exchanger was 35L/min. The temperature information of the hot water fluid entering and leaving the reactor was monitored. After the overall working conditions were stabilized, after the 60°C hot water passed through the reactor, the actual measured fluid temperature at the discharge port was 31°C, which was +1.0°C lower than the temperature of the heat exchanger jacket, and the error range was less than 4.0%.
实施例2对比实验Example 2 Comparative Experiment
在本实施例中,将反应管20内部设计成光滑无连续凸起结构,其余部件,如换热器10和11、转轴30、法兰盖40和41、法兰夹50~53都与实施例1相同。以此方案进行混合效果测试,采用植物油(流体一)、乳化剂(流体二)和水(流体三)三种流体在20~25℃条件下进料进行水乳剂的制备。植物油进料量为10mL/min,乳化剂为15mL/min,水进料量为30mL/min,三种流体从同一端的进料口进料,经过转轴的剪切力混合后得水乳剂,经分析检测油滴粒径约2.5μm。In this embodiment, the interior of the reaction tube 20 is designed to be smooth without continuous protrusions, and the remaining components, such as heat exchangers 10 and 11, shaft 30, flange covers 40 and 41, and flange clamps 50-53, are the same as those in Example 1. This scheme is used to test the mixing effect, and three fluids, vegetable oil (fluid one), emulsifier (fluid two) and water (fluid three), are fed at 20-25°C to prepare an aqueous emulsion. The feed rate of vegetable oil is 10mL/min, the emulsifier is 15mL/min, and the feed rate of water is 30mL/min. The three fluids are fed from the feed port at the same end, and the aqueous emulsion is obtained after mixing by the shear force of the shaft. The oil droplet size is about 2.5μm after analysis.
采用60℃水作为唯一流体从进料口注入反应器中,另一端出料口出来,流体流速为50mL/min,换热夹套温度设定为30℃,换热器中导热油流速为35L/min。监控热水流体进入 反应器和出反应器时的温度信息。待整体工况稳定之后,60℃热水经过反应器后,出料口实际测定的流体温度为35℃,与换热器夹套温度差距+5.0℃,误差范围在约17%。60℃ water is used as the only fluid to be injected into the reactor from the feed port and out of the other end of the discharge port. The fluid flow rate is 50mL/min, the heat exchange jacket temperature is set to 30℃, and the heat transfer oil flow rate in the heat exchanger is 35L/min. Monitor the temperature information of the hot water fluid entering and leaving the reactor. After the overall working conditions are stable, after the 60℃ hot water passes through the reactor, the actual measured fluid temperature at the discharge port is 35℃, which is +5.0℃ different from the heat exchanger jacket temperature, and the error range is about 17%.
实施例3对比实验Example 3 Comparative Experiment
在本实施例中,将换热器内部的刻槽取消,换热器内表面为光滑结构,其余部件,如反应管20、转轴30、法兰盖40和41、法兰夹50~53都与实施例1相同。采用60℃水作为唯一流体从进料口注入反应器中,另一端出料口出来,流体流速为50mL/min,换热夹套温度设定为30℃,换热器中导热油流速为35L/min。监控热水流体进入反应器和出反应器时的温度信息。待整体工况稳定之后,60℃热水经过反应器后,出料口实际测定的流体温度为31.5℃,与换热器夹套温度差距+1.5℃,误差范围小于5.0%。In this embodiment, the grooves inside the heat exchanger are removed, and the inner surface of the heat exchanger is a smooth structure. The remaining components, such as the reaction tube 20, the rotating shaft 30, the flange covers 40 and 41, and the flange clamps 50-53 are the same as those in Example 1. 60°C water is used as the only fluid to be injected into the reactor from the feed port and out of the other end of the discharge port. The fluid flow rate is 50mL/min, the heat exchange jacket temperature is set to 30°C, and the heat transfer oil flow rate in the heat exchanger is 35L/min. Monitor the temperature information of the hot water fluid when it enters and exits the reactor. After the overall working conditions are stable, after the 60°C hot water passes through the reactor, the actual measured fluid temperature at the discharge port is 31.5°C, which is +1.5°C different from the heat exchanger jacket temperature, and the error range is less than 5.0%.
对上述实施例1、实施例2、实施例3的结果进行对比,可知:1)采用本发明实施例提供的动态微通道管式连续反应器,其油水混合乳化效果相较于普通管式反应器表现更加优秀,在测试条件下,乳化油滴粒径降低了178%(0.9μm vs.2.5μm),整体乳化更加充分;2)反应管的凹凸设计,以及换热器的刻槽折返流设计,增加了反应器内部的换热面积,反应器的整体换热能力得到提升,在测试条件下,实施例1流体进口温度与换热器油的温度最接近,温度控制更加精准。By comparing the results of the above-mentioned Example 1, Example 2, and Example 3, it can be seen that: 1) The dynamic microchannel tubular continuous reactor provided by the embodiment of the present invention has a better oil-water mixing emulsification effect than that of the ordinary tubular reactor. Under the test conditions, the particle size of the emulsified oil droplets is reduced by 178% (0.9μm vs. 2.5μm), and the overall emulsification is more sufficient; 2) The concave-convex design of the reaction tube and the grooved reflux flow design of the heat exchanger increase the heat exchange area inside the reactor, and the overall heat exchange capacity of the reactor is improved. Under the test conditions, the fluid inlet temperature of Example 1 is closest to the temperature of the heat exchanger oil, and the temperature control is more precise.

Claims (8)

  1. 一种动态混合微通道连续流反应器,其特征在于,所述动态混合微通道连续流反应器包括反应管、转轴(30)、第一换热器(10)、第二换热器(11)、联轴器(60)和驱动装置(70);A dynamic mixing microchannel continuous flow reactor, characterized in that the dynamic mixing microchannel continuous flow reactor comprises a reaction tube, a rotating shaft (30), a first heat exchanger (10), a second heat exchanger (11), a coupling (60) and a driving device (70);
    反应管包括第一半反应管(20)和第二半反应管(21),反应管的内径大于转轴(30)的外径,转轴(30)以同轴的方式设置在反应管内部,驱动装置(70)配置为能够驱动转轴(30)与反应管相对做旋转运动;第一半反应管(20)和第二半反应管(21)为两个形状、尺寸相同的半圆柱,两者拼合在一起形成一个内部有圆柱形空间的反应管。The reaction tube comprises a first half reaction tube (20) and a second half reaction tube (21); the inner diameter of the reaction tube is greater than the outer diameter of the rotating shaft (30); the rotating shaft (30) is coaxially arranged inside the reaction tube; and the driving device (70) is configured to be able to drive the rotating shaft (30) and the reaction tube to perform relative rotational motion; the first half reaction tube (20) and the second half reaction tube (21) are two semi-cylinders of the same shape and size, and the two are assembled together to form a reaction tube with a cylindrical space inside.
  2. 根据权利要求1所述的动态混合微通道连续流反应器,其特征在于,由第一半反应管(20)和第二半反应管(21)拼合后组成的反应管内表面设置至少一个挡台,挡台呈圆周状紧贴反应管内表面,反应管内表面的至少一个挡台高度介于3.0~20.0mm,在挡台上设置至少一个凹陷,凹陷的深度为1.00~3.00mm;The dynamic mixing microchannel continuous flow reactor according to claim 1 is characterized in that at least one baffle is provided on the inner surface of the reaction tube formed by splicing the first half reaction tube (20) and the second half reaction tube (21), the baffle is circular and close to the inner surface of the reaction tube, the height of at least one baffle on the inner surface of the reaction tube is between 3.0 and 20.0 mm, and at least one depression is provided on the baffle, and the depth of the depression is 1.00 to 3.00 mm;
    优选的,第一半反应管(20)和第二半反应管(21)通过横向部位的螺栓进行整体固定,且两者径向贴合面设置有密封垫片。Preferably, the first half reaction tube (20) and the second half reaction tube (21) are integrally fixed by bolts at a transverse position, and a sealing gasket is provided on the radial fitting surfaces of the two.
  3. 根据权利要求2所述的动态混合微通道连续流反应器,其特征在于,转轴(30)上设置至少一个挡台,挡台呈圆周状紧贴转轴(30)的表面,转轴(30)上的至少一个挡台高度介于3.0~20.0mm,在挡台上设置至少一个凹陷,凹陷的深度为1.00~3.00mm;The dynamic mixing microchannel continuous flow reactor according to claim 2 is characterized in that at least one baffle is provided on the rotating shaft (30), the baffle is circular and close to the surface of the rotating shaft (30), the height of at least one baffle on the rotating shaft (30) is between 3.0 and 20.0 mm, and at least one depression is provided on the baffle, and the depth of the depression is 1.00 to 3.00 mm;
    反应管内表面设置的至少一个挡台与转轴(30)上设置的至少一个挡台相互错开,使得反应管与转轴(30)之间的旋转运动不受影响;转轴(30)上设置的至少一个挡台不与反应管的内表面接触;反应管内表面设置的至少一个挡台不与转轴(30)表面接触。At least one stopper arranged on the inner surface of the reaction tube and at least one stopper arranged on the rotating shaft (30) are staggered with each other, so that the rotational movement between the reaction tube and the rotating shaft (30) is not affected; at least one stopper arranged on the rotating shaft (30) does not contact the inner surface of the reaction tube; and at least one stopper arranged on the inner surface of the reaction tube does not contact the surface of the rotating shaft (30).
  4. 根据权利要求1-3任一项所述的动态混合微通道连续流反应器,其特征在于,反应管内表面设置至少两个挡台,至少两个挡台沿径向彼此间隔开,设置在反应管内表面;The dynamic mixing microchannel continuous flow reactor according to any one of claims 1 to 3, characterized in that at least two baffles are arranged on the inner surface of the reaction tube, and the at least two baffles are spaced apart from each other in the radial direction and arranged on the inner surface of the reaction tube;
    优选的,反应管内表面设置3组以上挡台,例如设置3-20个,例如30个、50个、甚至100个;每一个挡台上设置3-30个凹陷,优选5-25个,优选6-12个,进一步优选8-10个;Preferably, more than 3 groups of baffles are arranged on the inner surface of the reaction tube, for example, 3-20, for example, 30, 50, or even 100 baffles are arranged; 3-30 recesses are arranged on each baffle, preferably 5-25, preferably 6-12, and further preferably 8-10;
    优选的,每一个挡台包括至少两个凹陷,上述至少两个凹陷均匀设置在挡台上;Preferably, each baffle comprises at least two recesses, and the at least two recesses are evenly arranged on the baffle;
    优选的,反应管内表面设置6个挡台,6个挡台沿径向彼此间隔开,设置在反应管内表面;每一个挡台包括8个凹陷,上述8个凹陷均匀设置在同一个挡台上;同一个挡台内部, 凹陷深度为1.0~3.0mm,宽度为1.0~3.0mm,凹陷呈长方体形,长度介于2.0~10.0mm,挡台高度介于3.0~20.0mm,一个挡台与另一个挡台之间的间隔为4.0~22.0mm。Preferably, 6 baffles are arranged on the inner surface of the reaction tube, and the 6 baffles are spaced apart from each other in the radial direction and arranged on the inner surface of the reaction tube; each baffle includes 8 depressions, and the above 8 depressions are evenly arranged on the same baffle; inside the same baffle, the depression has a depth of 1.0 to 3.0 mm and a width of 1.0 to 3.0 mm. The depression is in the shape of a rectangular parallelepiped with a length of 2.0 to 10.0 mm. The height of the baffle is between 3.0 and 20.0 mm, and the interval between one baffle and another is 4.0 to 22.0 mm.
  5. 根据权利要求1-4任一项所述的动态混合微通道连续流反应器,其特征在于,转轴(30)的表面设置至少两个挡台,至少两个挡台沿径向彼此间隔开,设置在转轴(30)表面;The dynamic mixing microchannel continuous flow reactor according to any one of claims 1 to 4, characterized in that at least two baffles are arranged on the surface of the rotating shaft (30), and the at least two baffles are spaced apart from each other in the radial direction and are arranged on the surface of the rotating shaft (30);
    优选的,转轴(30)表面设置3组以上挡台,例如设置3-20个,例如30个、50个、甚至100个;每一个挡台上设置3-30个凹陷,优选5-25个,优选6-12个,进一步优选8-10个;Preferably, more than three groups of baffles are arranged on the surface of the rotating shaft (30), for example, 3-20, for example, 30, 50, or even 100; 3-30 recesses are arranged on each baffle, preferably 5-25, preferably 6-12, and further preferably 8-10;
    优选的,每一个挡台包括至少两个凹陷,上述至少两个凹陷均匀设置在转轴(30)同一径向位置的表面;Preferably, each stopper comprises at least two recesses, and the at least two recesses are evenly arranged on the surface of the rotating shaft (30) at the same radial position;
    优选的,转轴(30)表面设置6个挡台,6个挡台沿径向彼此间隔开,设置在转轴(30)表面;Preferably, six baffles are arranged on the surface of the rotating shaft (30), and the six baffles are spaced apart from each other in the radial direction and arranged on the surface of the rotating shaft (30);
    优选的,每一个挡台包括8个凹陷,上述8个凹陷均匀设置在同一挡台上;同一个挡台内部,凹陷宽度1.0~3.0mm,凹陷深度为1.0~3.0mm,凹陷呈长方体形,长度介于2.0~10.0mm,挡台高度介于3.0~20.0mm,一个挡台与另一个挡台之间的间隔为4.0~22.0mm。Preferably, each baffle includes 8 depressions, and the above 8 depressions are evenly arranged on the same baffle; inside the same baffle, the depression width is 1.0-3.0 mm, the depression depth is 1.0-3.0 mm, the depression is rectangular in shape, the length is between 2.0-10.0 mm, the baffle height is between 3.0-20.0 mm, and the interval between one baffle and another is 4.0-22.0 mm.
  6. 根据权利要求1-5任一项所述的动态混合微通道连续流反应器,其特征在于,第一换热器(10)和第二换热器(11)拼合后为一圆筒,该圆筒内径与反应管的外径相同,且该圆筒长度与反应管长度相等;The dynamic mixing microchannel continuous flow reactor according to any one of claims 1 to 5, characterized in that the first heat exchanger (10) and the second heat exchanger (11) are assembled into a cylinder, the inner diameter of the cylinder is the same as the outer diameter of the reaction tube, and the length of the cylinder is equal to the length of the reaction tube;
    优选的,第一换热器(10)和第二换热器(11)紧密贴合在反应管外侧,由第一外圈法兰夹(50)、第二外圈法兰夹(51)、第三外圈法兰夹(52)、第四外圈法兰夹(53)固定在反应管上;Preferably, the first heat exchanger (10) and the second heat exchanger (11) are tightly fitted on the outside of the reaction tube and are fixed on the reaction tube by a first outer ring flange clamp (50), a second outer ring flange clamp (51), a third outer ring flange clamp (52), and a fourth outer ring flange clamp (53);
    优选的,在第一换热器(10)和第二换热器(11)相互贴合之处,以及在第一换热器(10)和第二换热器(11)两端与反应管贴合之处设置密封垫;Preferably, a sealing gasket is provided at the place where the first heat exchanger (10) and the second heat exchanger (11) are attached to each other, and at the places where both ends of the first heat exchanger (10) and the second heat exchanger (11) are attached to the reaction tube;
    优选的,第一换热器(10)和第二换热器(11)内壁具有刻槽型通路,通路宽5.0~20.0mm,深2.0~20.0mm;Preferably, the inner walls of the first heat exchanger (10) and the second heat exchanger (11) have grooved passages, the passages are 5.0 to 20.0 mm wide and 2.0 to 20.0 mm deep;
    优选的,第一换热器(10)和第二换热器(11)两端分别有一个进/出液口,供导热流体进/出,第一法兰盖(40)和第二法兰盖(41)安装在反应管两端并密封反应管;Preferably, the first heat exchanger (10) and the second heat exchanger (11) are provided with a liquid inlet/outlet at both ends for the heat transfer fluid to enter/exit, and the first flange cover (40) and the second flange cover (41) are installed at both ends of the reaction tube and seal the reaction tube;
    优选的,转轴(30)一端穿过第一法兰盖(40)的中心孔,另一端穿过第二法兰盖(41)的中心孔,通过连轴器(60)与驱动装置(70)的动力输出轴相连接。Preferably, one end of the rotating shaft (30) passes through the center hole of the first flange cover (40), and the other end passes through the center hole of the second flange cover (41), and is connected to the power output shaft of the driving device (70) through a coupling (60).
  7. 根据权利要求6所述的动态混合微通道连续流反应器,其特征在于,在第一法兰盖(40)上设置四个进/出料口:第一进/出料口(400),第二进/出料口(401),第三进/出料口(402),第四进/出料口(403),这四个进/出料口同时也可以作为探温口;The dynamic mixing microchannel continuous flow reactor according to claim 6 is characterized in that four inlet/outlet ports are arranged on the first flange cover (40): a first inlet/outlet port (400), a second inlet/outlet port (401), a third inlet/outlet port (402), and a fourth inlet/outlet port (403), and these four inlet/outlet ports can also be used as temperature probe ports;
    优选的,在第二法兰盖(41)上设置四个进/出料口:第五进/出料口(410),第六进/出料口(411),第七进/出料口(412)、第八进/出料口(413)。Preferably, four inlet/outlet ports are provided on the second flange cover (41): a fifth inlet/outlet port (410), a sixth inlet/outlet port (411), a seventh inlet/outlet port (412), and an eighth inlet/outlet port (413).
  8. 根据权利要求1-7任一项所述的动态混合微通道连续流反应器,其特征在于,驱动装置(70)配置为能够驱动转轴(30)与反应管相对做旋转运动;The dynamic mixing microchannel continuous flow reactor according to any one of claims 1 to 7, characterized in that the driving device (70) is configured to drive the rotating shaft (30) and the reaction tube to perform relative rotational motion;
    优选的,驱动装置(70)的输出轴通过联轴器(60)与转轴(30)同轴连接,于是驱动装置(70)旋转时能够带动转轴(30)一起旋转。Preferably, the output shaft of the driving device (70) is coaxially connected to the rotating shaft (30) via a coupling (60), so that when the driving device (70) rotates, it can drive the rotating shaft (30) to rotate together.
PCT/CN2022/121198 2022-09-26 2022-09-26 Dynamic combined micro-channel continuous flow reactor WO2024065074A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140073498A1 (en) * 2012-09-06 2014-03-13 Eppendorf Ag Rotor Device, Centrifuge Bowl, and Centrifuge, and the Production Method Thereof
CN105854685A (en) * 2016-06-15 2016-08-17 浙江大学 Dynamic cell printing micromixer
CN110548463A (en) * 2019-08-27 2019-12-10 济南泺沣医药科技有限公司 continuous flow reaction module and device
CN211436155U (en) * 2019-11-22 2020-09-08 江苏方圆芳纶研究院有限公司 Micro-reactor
CN112403414A (en) * 2020-11-16 2021-02-26 徐州亚兴医疗科技有限公司 Micro-channel continuous catalytic device and working method thereof
CN114632487A (en) * 2022-03-29 2022-06-17 浙江工业大学 Micro-channel super-gravity rotating bed

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140073498A1 (en) * 2012-09-06 2014-03-13 Eppendorf Ag Rotor Device, Centrifuge Bowl, and Centrifuge, and the Production Method Thereof
CN105854685A (en) * 2016-06-15 2016-08-17 浙江大学 Dynamic cell printing micromixer
CN110548463A (en) * 2019-08-27 2019-12-10 济南泺沣医药科技有限公司 continuous flow reaction module and device
CN211436155U (en) * 2019-11-22 2020-09-08 江苏方圆芳纶研究院有限公司 Micro-reactor
CN112403414A (en) * 2020-11-16 2021-02-26 徐州亚兴医疗科技有限公司 Micro-channel continuous catalytic device and working method thereof
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