CN108993342B - Micro-mixing system and method for photochemical reaction in tubular reactor - Google Patents
Micro-mixing system and method for photochemical reaction in tubular reactor Download PDFInfo
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- CN108993342B CN108993342B CN201811038708.0A CN201811038708A CN108993342B CN 108993342 B CN108993342 B CN 108993342B CN 201811038708 A CN201811038708 A CN 201811038708A CN 108993342 B CN108993342 B CN 108993342B
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- 238000002156 mixing Methods 0.000 title claims abstract description 94
- 238000006552 photochemical reaction Methods 0.000 title claims abstract description 83
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
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- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000009652 hydrodynamic focusing Methods 0.000 claims description 2
- 238000005728 strengthening Methods 0.000 claims description 2
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- 229930003316 Vitamin D Natural products 0.000 description 1
- QYSXJUFSXHHAJI-XFEUOLMDSA-N Vitamin D3 Natural products C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C/C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-XFEUOLMDSA-N 0.000 description 1
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- QYSXJUFSXHHAJI-YRZJJWOYSA-N vitamin D3 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-YRZJJWOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00889—Mixing
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00891—Feeding or evacuation
- B01J2219/00894—More than two inlets
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00925—Irradiation
- B01J2219/0093—Electric or magnetic energy
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a micro-mixing system and a method for photochemical reaction in a tubular reactor, which are characterized in that the system consists of a micro-mixing unit and a tubular photochemical reaction device, wherein the micro-mixing unit is connected with the tubular photochemical reaction device in series, and in the micro-mixing unit, a gas phase or liquid carrier phase which is not compatible with a reaction liquid shears the reaction liquid into a liquid column. Has great prospect in the industrial application of photochemical reaction.
Description
Technical Field
The invention belongs to the field of organic photochemical synthesis, and particularly relates to a micro-mixing system and a micro-mixing method for photochemical reaction in a tubular reactor.
Background
Photochemical reactions are due to their property of using photons to initiate chemical reactions and to promote molecular transformations [ Scholes, g.d.; fleming, g.r.; olaya-Castro, a.; van Grondelle, r., nat. Chem.2011,3,763]Has the advantages of green process, low pollution and the like, and has been widely paid attention to and studied by people in the past decades. However, due to the limitations of equipment conditions and photon attenuation, the photochemical production has serious problems of low light energy utilization rate, difficult equipment amplification and the like [ Su, Y.; straathof, n.j.w.; hessel, v.; noe ·· l,T.,Chem.-Eur.J.2014,20,10562]. In particular, amplification of the device is made difficult by the rapid decay of photons in the liquid with the liquid layer thickness (langerhans law). On one hand, the photon utilization rate is low due to the increase of the liquid layer thickness by adopting a volume amplification mode, and the reaction time is obviously increased; on the other hand, the product is simultaneously in the liquid phase, which is easy to cause by-productsThe formation of matter even presents problems of excessive illumination.
Researchers have employed various methods to enhance photochemical reactions, increase turbulence within fluids, and improve uniformity of reactant concentration profiles. On the one hand, the improvement of the traditional equipment is that the internal mixing of the solution is enhanced by the way of gas bubbling and atomization of the reaction solution; on the other hand, in recent years (microchannel) tubular reactors, which have been developed in combination with continuous flow technology, have also received increasing attention. For example, chinese patent CN1445215a uses an inward immersion nitrogen bubbling method to enhance the internal mixing of solutions, chinese patent CN202238034U uses a built-in atomizer to increase vitamin D 3 The illumination intensity in the synthesis process; photochemical synthesis of vitamin D by Chinese patent CN103553993A using homogeneous microfluid tube reactor 3 Continuous operation of the photochemical synthesis process is realized. However, the gas bubbling mode has limited disturbance intensity in the solution, the atomization method still cannot avoid the problem of light intensity attenuation away from the light source, meanwhile, the method still depends on kettle type equipment, reaction products cannot move out of the system, and the problems of excessive illumination and side reaction still exist. While the tubular reactor can avoid the problem of volume enlargement by a number enlarging method of a plurality of devices connected in parallel. However, the tubular reactor still adopts homogeneous reaction liquid to flow, mass transfer can only be carried out through molecular diffusion in boundary layers at the tube wall, reactants are difficult to effectively migrate to the wall surface of the device to receive light, products are difficult to rapidly separate from the wall surface of the device to prevent excessive light from generating byproducts [ Knowles, J.P., elliott, L.D., booker-Milburn K.I., beilstein J.Org.chem.2012,8,2025.)]The method comprises the steps of carrying out a first treatment on the surface of the The homogeneous phase flow has the characteristics of high flow velocity distribution and low circumference, can cause the difference of residence time of reactants in the reactor, and does not completely solve the problem of excessive illumination; in addition, many microchannel-grade tubular reactor flows are typically on the order of microliters per minute, and the reaction efficiency is low.
In recent years, for some micro-channel, tubular reactor organic synthesis systems, attempts have been made to obtain a liquid column flow of the reaction liquid by the separation of the liquid or gas, which is immiscible with the reaction liquid, as a carrier phase, thereby ensuring a substantially uniform residence time of the reactants in each liquid column [ Porta, R., benaglia, M., puglisi A., org.process.Res.Dev.2016,20,2]. The method can effectively strengthen the synthesis process and improve the process controllability for common organic synthesis, but does not solve the problem of uneven illumination for photochemical reaction, and the mixing strength in the liquid column of the reaction liquid is still to be further improved. The core problem of the tubular reactor is that the reaction liquid is always positioned at a position opposite to the light source, and only the energy of photons after passing through the liquid layer can be obtained, and the winding mode of the conventional tubular reactor is not changed for the light source. In addition, the radius of curvature of the tube wrap is typically much larger than the tube inner diameter, resulting in an overstable liquid column flow with a low degree of internal turbulence.
Disclosure of Invention
In view of the above, the present invention proposes to solve the above problems by the migration of the light source position by the reaction liquid phase in combination with the enhanced mixing structure of the reactor. Specifically, the invention provides a micro-mixing system for photochemical reaction in a tubular reactor with a reverse structure, which is characterized by comprising a micro-mixing unit and a tubular photochemical reaction device, wherein the micro-mixing unit is connected with the tubular photochemical reaction device in series, as shown in figure 1. In the micro-mixing unit, a carrier phase fluid that is not compatible with the reaction liquid shears the reaction liquid into a liquid column.
Further, it is characterized in that: the micro-mixing units are T-shaped, Y-shaped, cross-flow shearing type, hydrodynamic focusing type or coaxial annular pipe type and coaxial improved type (the diameter of a cavity formed by dispersed liquid drops is larger than that of a tubular reactor as shown in figure 2) micro-channel devices.
Preferably, coaxial tube and coaxial collar modified microchannel members; it is further preferred that the contact angle of the inner wall of the inner tube with the carrier phase fluid is greater than 150 ° in the coaxial grommet and the coaxial grommet modification; further preferably, the contact angle between the inner wall of the inner tube of the improved coaxial ring tube and the carrier fluid is more than 150 DEG, the inner diameter of a cavity formed by liquid drops is D, and the inner diameter of the inner dispersing tube is D d And the inner diameter D of the tubular reactor is satisfied, 10D d >D>2D d ，2D d >d>0; further preferably 2D d <D<3D d ，2D d >d>D d 。
Further, it is characterized in that: the micro-mixing unit equipment is made of polymer, stainless steel, inorganic glass or a mixture of the above materials, and the channel size is 0.05-50 mm.
Further, it is characterized in that: the tubular photochemical reaction device comprises a tubular reactor and a light source, wherein the reactor can be any tubular reactor which is transparent. The number of light sources and the length of the tubular reactor are dependent on the illumination time required for the photochemical reaction.
Further, it is characterized in that: the tubular reactor is made of perfluoroethylene propylene copolymer, polytetrafluoroethylene, quartz glass, silicate glass, borosilicate glass or a mixture thereof, and the inner diameter of the tubular reactor is 0.05-50 mm; the light source is a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a Light Emitting Diode (LED) lamp or the combination thereof, and the light emitted by the light source is ultraviolet light, visible light, infrared light or the combination thereof; the cold trap is made of quartz glass, silicate glass, high borosilicate glass or a mixture of the quartz glass and the silicate glass.
Further, the tubular reactor comprises 1 and more than 1 reversing or strengthening mixing structures in a winding mode. The structure of the single inversion is shown in fig. 3. Taking a tubular reactor with a built-in light source as an example, the tubular reactor is in a spiral winding structure with a certain angle (preferably 180 degrees) with the axial direction of the tubular reactor in the process of winding in a spiral mode. Due to the action of centrifugal force, the spiral winding causes that all parts of the liquid column in the pipe are subjected to different magnitudes of the centrifugal force, and internal circulation or secondary flow exists; the structure can make the liquid column in the tubular reactor circularly rotate for the same angle, thus improving the more uniform light receiving of the reaction liquid in the liquid column, further avoiding excessive light, reducing the time required by photochemical reaction and improving the selectivity of the product and the light utilization rate.
More preferably, the reinforced hybrid structure may be, but is not limited to, annular ear and columnar rib type, as shown in fig. 4. The structure is that the secondary flow or internal circulation in the liquid column is turned (preferably +/-90 degrees), so that the mixing in the liquid column is enhanced, the mixing in the liquid column is more uniform, excessive illumination is similarly avoided, and the selectivity of the product and the light utilization rate are improved. The external light source tubular reactor has reinforced mixing structure at 90 deg. to the original layout plane.
The invention also provides a method for carrying out photochemical reaction in a tubular reactor with a reversing structure, which is characterized by comprising the following steps:
(1) In the micro-mixing unit, liquid or gas which is not mutually soluble with photochemical reaction liquid is used as carrier phase fluid, and the liquid column fluid is obtained by adjusting the flow rate of two phases and shearing the liquid phase fluid into a liquid column;
(2) The obtained liquid column flow enters a tubular reactor to receive illumination, and the illumination reaction occurs in the liquid column of the reaction liquid. In the illumination process, the reaction liquid always keeps liquid column type flowing.
(3) The liquid column flow passes through the tubular reactor once or circulates for many times, the total residence time is controlled according to the reaction progress, and the product solution is obtained after phase separation.
Further, the reaction solution is a solution containing a photochemical reaction component.
Further characterized in that the flow ratio of the carrier phase to the reaction liquid phase is 1: 20-20: 1, a step of; the carrier phase comprises: the electrolyte solution, silicone oil, alkanes and other liquids, or nitrogen, argon and other gases, i.e. liquids or gases which are not compatible with the reaction solution, can be used as the carrier phase.
The invention has the advantages that:
the fluid which is not mutually dissolved with the reaction liquid is introduced as a carrying phase, the reaction liquid is sheared into a liquid column by utilizing a micro-mixing unit through cross flow, parallel flow and other forms, and the liquid column enter a tubular reactor in a tubular photochemical reaction device together to receive illumination and react. In the illumination process, the reaction liquid always keeps liquid column type flowing, strong circulation flow exists in the liquid column, the thickness of a boundary layer of the reaction liquid can be greatly reduced, reactants at all positions in the liquid column are promoted to be illuminated, the residence time of the reaction liquid is ensured to be basically consistent by a carrying phase fluid separation method, and the phenomenon that products are accumulated at the wall surface and excessively illuminated to generate byproducts is avoided. Meanwhile, by means of the inversion and reinforced mixing structure of the tubular reactor, the migration of the reaction liquid at the position far away from the light source to the side close to the light source is promoted, and the internal mixing of the reaction liquid is reinforced. On one hand, the residence time of each section of reaction liquid column is ensured to be consistent, the thickness of a boundary layer is effectively reduced, and the conversion rate and the yield of photochemical reaction are improved; on the other hand, the pipe diameter and the system flow can be properly increased by means of stronger internal circulation in the liquid column, and the treatment capacity of the reaction system is improved.
Drawings
FIG. 1 is a schematic diagram of a micro-hybrid system for photochemical reactions within a tubular reactor according to the invention;
FIG. 2 is a schematic diagram of various forms of microchannel devices in a micro-hybrid cell, wherein A is T-shaped; b is Y-type; c is cross flow shearing type; d is hydraulic focusing; e is a coaxial ring pipe type; f is an improved coaxial tube type;
FIG. 3 is a schematic diagram of a single inversion and enhanced mixing configuration for a tubular reactor.
FIG. 4 is a schematic diagram of a tubular reactor and enhanced mixing structure, wherein A is a loop; b is rib type.
FIG. 5 is a schematic diagram of a conventional tubular reactor without a reversing structure.
Detailed Description
The features of the present invention and other related features are described in further detail below by way of example in conjunction with the following drawings, to facilitate understanding by those skilled in the art:
the micro-mixing system for photochemical reaction in the tubular reactor comprises a micro-mixing unit and a tubular photochemical reaction device, wherein the micro-mixing unit is connected with the tubular photochemical reaction device in series, namely, the inlet of the tubular reactor is connected with the outlet of the micro-mixing unit, and the outlet of the tubular reactor is used for collecting products, as shown in figure 1.
The micro-mixing unit comprises a micro-channel device, wherein the micro-channel device comprises a reaction liquid channel, a carrier phase fluid channel, a liquid drop forming cavity and an output pipeline, one end of the reaction liquid channel and one end of the carrier phase fluid channel are inlets of reaction liquid or carrier phase fluid, the other end of the reaction liquid channel and one end of the carrier phase fluid channel are communicated with the liquid drop forming cavity, the reaction liquid and the carrier phase fluid are subjected to intersection shearing mixing in the liquid drop forming cavity to form a liquid column flow, and the liquid column flow flows from the liquid drop forming cavity to the rear output pipeline. The output pipeline is connected with the tubular photochemical reaction device. Preferably, the droplet forming chamber and the outlet conduit have the same inner diameter. Preferably, the carrier phase channel may have one, two or more.
Wherein; the micro-mixing unit is a micro-channel device, and the micro-mixing unit can be in a T-type, a Y-type, a cross-flow shearing type, a hydraulic focusing type, a coaxial loop type and the like (as shown in fig. 2). Preferably, the micro-mixing unit equipment is made of polymer, stainless steel, inorganic glass or a mixture of the polymer and the inorganic glass, and the channel size of the micro-mixing unit equipment is 0.05-50 mm. More preferably, the contact angle between the inner wall of the inner tube of the coaxial annular tube and the carrier phase fluid is greater than 150 degrees.
The T-shaped structure is that the carrying phase channel, the liquid drop forming cavity and the output pipeline are of a linear structure, and the reaction liquid channel is perpendicular to the carrying phase channel.
The Y-shaped structure is that the carrying phase channel and the reaction liquid channel respectively form two sides of the top end of the Y shape, and the liquid drop forming cavity and the output pipeline are of a linear structure to form the lower end of the Y shape.
The cross flow shearing type structure comprises two carrying phase channels, the two carrying phase channels are arranged in 180 degrees in opposite directions, the reaction liquid channels are perpendicular to the carrying phase channels, the liquid drop forming cavity is arranged at the junction of the two carrying phase channels and the reaction liquid channels, and the output pipeline and the reaction liquid channels are in a straight line.
The hydraulic focusing structure is different from the cross-flow shearing structure in that the liquid drop forming cavity is also provided with a diameter reducing part between the liquid drop forming cavity and the connecting part of the output pipeline so as to ensure the formation of liquid drops of the carrying phase.
The coaxial ring pipe type structure comprises two carrying phase channels, the two carrying phase channels are oppositely arranged at 180 degrees, and the liquid drop forming cavity and the output pipeline are of a linear structure and are perpendicular to the two carrying phase channels. The reaction liquid channel vertically passes through the two carrying phase channels and extends into the liquid drop forming cavity.
More preferably, the microchannel device may employ a coaxial loop modified structure in which a carrying phase channel is connected in-line with a droplet formation chamber and an output channel, and a reaction liquid channel extends perpendicularly from a side wall of the droplet formation chamber, and a front end thereof turns toward a liquid column flow direction. Wherein the inner diameter of the carrying phase channel is the same as the diameter of the output channel, and d is the same as the diameter of the output channel; the inner diameter of the droplet forming chamber is D; the inner diameter of the reaction liquid channel is D d . Wherein, the inner diameter D of the liquid drop forming cavity and the inner diameter D of the reaction liquid channel d And the inner diameter d of the output channel satisfies: 10D (10D) d >D>2D d ，2D d >d>0; further preferably 2D d <D<3D d ，2D d >d>D d . It is further preferred that the contact angle of the inner wall of the inner tube with the dispersed phase liquid in the coaxial grommet and the coaxial grommet modification is more than 150 °; it is further preferred that the inner wall of the inner tube of the improved coaxial collar has a contact angle with the dispersed phase liquid of more than 150 °. The structure can ensure that the droplet length of the carrier liquid is strictly controlled and is not influenced by the flow of the reaction liquid phase.
Wherein, the tubular photochemical reaction device comprises a tubular reactor, a light source and a cold trap. When the tubular reactor is in a spreading shape, the light source irradiates the reactor on one side; when the tubular reactor is wound in a coil shape, a light source (e.g., a lamp tube) is placed in the middle of the tubular reactor. If the light source emits heat seriously, and the temperature exceeds the light reaction requirement temperature, a cold trap needs to be arranged between the light source and the tubular reactor, and the cold trap material depends on the wavelength range required by the photochemical reaction.
Wherein the tubular reactor is made of perfluoroethylene propylene copolymer, polytetrafluoroethylene, quartz glass, silicate glass, high borosilicate glass or a mixture thereof, and the inner diameter of the tubular reactor is 0.05-50 mm; the light source is a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a Light Emitting Diode (LED) lamp or the combination thereof, and the light emitted by the light source is ultraviolet light, visible light, infrared light or the combination thereof; the cold trap is made of quartz glass, silicate glass, high borosilicate glass or a mixture of the quartz glass and the silicate glass.
The tubular reactor comprises 1 or more turning structures which are different from the winding direction in a winding mode, wherein the turning structures are formed by winding the tubular reactor on parts outside the light source main body, and the parts outside the light source main body can be branch structures extending out of the light source main body or parts outside the light source main body. In particular, the turning structure comprises a reversing structure or a reinforced mixing structure.
The reversed structure is shown in fig. 3, which means that the tubular reactor is turned at a certain angle in the spiral winding process. The turn is preferably greater than 30 °, more preferably greater than 90 °, and most preferably a 180 ° turn configuration. Due to the action of centrifugal force, the spiral winding causes that all parts of the liquid column in the pipe are subjected to different magnitudes of the centrifugal force, and internal circulation or secondary flow exists; there are typically two internal loops formed within the liquid column or droplet: the inner circulation is respectively close to one side of the spiral center and the inner circulation is far from one side of the spiral center. For tubules wound around a tubular reactor, the internal circulation formed inside the column of liquid includes one internal circulation near the tube and one internal circulation far from the tube, with the two internal circulation columns circulating within the respective internal circulation without substantially circulating with the other internal circulation. Without the inversion structure, the positions of the two inner loops are relatively fixed-similar to the near ground and the far ground of the moon, the inner loop of the near light surface always receives direct irradiation of the ultraviolet lamp tube, and the inner loop of the far light surface receives low ultraviolet irradiation probability. As shown in fig. 3, a supporting structure (the supporting structure may be a part of the light source main body or a structure outside the light source, which may be connected or disconnected with the light source) is arranged outside the light source main body, the tubular reactor is wound on the supporting structure from the light source main body and returns to the light source main body, so that the positions of the near-light tube part and the far-light tube part of the liquid column in the tubular reactor are exchanged, that is, the supporting structure adds 180 degrees of turning to the liquid column, so that the positions of the two internal loops are exchanged, and the internal loop of the far-light tube is originally close to the light tube side and is irradiated by the ultraviolet light tube; while the inner loop originally near the tube is far away. Therefore, the probability that each part in the liquid drop is irradiated by the ultraviolet lamp is more uniform, excessive irradiation is further avoided, the time required by photochemical reaction is reduced, and the selectivity of the product and the light utilization rate are improved. Wherein preferably the turning angle is controlled by the angle of the in-going and out-going portions when the tubular reactor is wound on the support structure.
Further, the reinforced mixing structure is shown in fig. 4, and means a spiral winding structure of a tubular reactor which is added in a spiral winding process and forms an included angle with the axial direction, wherein the absolute value of the angle is preferably greater than 30 degrees, more preferably greater than 60 degrees, and most preferably 90 degrees. Taking the example of a tubular reactor with built-in light source, the tubular reactor is spirally wound on the light source body during the spiral winding, the tubular reactor is added at an angle (preferably + -90 DEG) to its axial direction (preferably, the branched structure is a part of the light source), and the tubular reactor is spirally wound on it for a plurality of turns, for example, three or more turns, preferably. From the foregoing description, there are generally two internal circuits formed within a liquid column or droplet: the inner circulation is respectively an inner circulation close to one side of the spiral center and an inner circulation far from one side of the spiral center; the addition of the branching structure in fig. 4 can make the liquid column in the tubular reactor rotate by the same angle, thus, after the reinforcing part rotates, two inner loops in the tubular reactor are respectively formed by one part to form a new inner loop, and the other part of the two inner loops forms another new inner loop (when the rotating angle is 90 degrees, the two inner loops are respectively divided into two equal halves and respectively combined to form two new inner loops), thus, the mixing in the liquid column can be reinforced, the mixing in the liquid column is more uniform, the more uniform illumination receiving of the reaction liquid in the liquid column is further improved, and when the tubular reactor returns to the light source main body from the reinforcing structure, the rotation is further carried out, so that the inner loops in the liquid column are further adjusted, the mixing in the liquid column is more uniform, the excessive illumination is further avoided, the time required by photochemical reaction is reduced, and the selectivity and the light utilization rate of the product are improved.
The reinforced mixing structure is preferably but not limited to a ring-ear type and a columnar rib type, as shown in fig. 4, wherein the ring-ear type is formed by connecting an oblong or oblong annular or similar shaped component on the outer surface of the light source, the long axis of the oblong or oblong shaped structure is preferably perpendicular to the axial direction, and the tubular reactor winds the annular component when encountering the annular component during the winding along the light source; the columnar rib structure is formed by projecting a sheet or a rod on the outer surface of the light source, the projecting angle is preferably perpendicular to the light source, and the tubular reactor is wound when passing through. Of course, the reinforced mixing structure is not limited to the above-listed structure, and may be any spiral winding structure having a certain angle with respect to the axial direction. Similarly, in a tubular reactor with an external light source, the intensified mixing structure is at an angle to the original layout plane, preferably 90 °. The number of the reinforced mixing structures can be one, two or more than three.
The working method of the micro-mixing system for photochemical reaction in the tubular reactor comprises the following steps:
(1) Introducing the reaction liquid and a carrier phase fluid into a micro-mixing unit, wherein the carrier phase fluid is a liquid or gas which is not mutually soluble with the reaction liquid; the flow of the carrying phase and the flow of the reaction liquid are regulated, the carrying phase fluid shears the reaction liquid into liquid columns in the form of cross flow, parallel flow and the like, and liquid column flow is formed, namely, the reaction liquid columns are separated by the carrying phase fluid, so that the fusion of the reaction liquid columns is avoided, and the flow of the carrying phase fluid drives the two-phase liquid column flow to integrally move;
(2) The liquid column flow enters a tubular reactor in a tubular photochemical reaction device to receive illumination, react and strengthen the internal mixing of the liquid column through the pipeline layout mixing; in the illumination process, the reaction liquid always keeps liquid column type flowing;
(3) The liquid column flow passes through the tubular reactor once or circulates for many times, the total residence time is controlled according to the reaction progress, and the product solution is obtained after phase separation.
Preferably, the reaction solution is a solution containing a photochemical reaction component.
Wherein, preferably, the carrier phase comprises: the electrolyte solution, silicone oil, alkane and other liquid, or nitrogen, i.e. gas or liquid which is not compatible with the reaction liquid, can be used as the carrier phase.
Preferably, the flow ratio of the carrier phase to the reaction liquid phase is 1: 20-20: 1, a step of;
example 1:
the micro-mixing system with the reversed structure for the photochemical reaction in the tubular reactor of the embodiment 1 of the invention consists of a micro-mixing unit and a tubular photochemical reaction device (comprising the tubular reactor and a light source).
The micro-mixing unit is of a T-shaped structure, the inner diameter of the main channel is 1mm, and the inner diameter of the side channel is 0.05mm; the light source is a lamp band formed by a 50W LED lamp bead array, and the wavelength is 475nm; the tubular reactor is a perfluoroethylene propylene copolymer tube with an inner diameter of 1mm and an outer diameter of 2mm, and is wound in the manner shown in FIG. 3; the light source lamp strip is arranged outside the tubular reactor, the light source lamp strip and the tubular reactor are coaxial, and the light source lamp strip and the tubular reactor are also in a spiral winding mode, and the distance between the control pipe wall and the LED lamp strip is 1cm (the outside of the tubular reactor which does not surround the axial center part is not wound with the LED lamp strip).
The micro-mixing system of photochemical reaction in the liquid column flow reinforced tubular reactor is utilized to carry out photochemical reaction to degrade Cr 6+ The ion steps are as follows:
1) Preparation of Cr 6+ 10mL of an aqueous solution having an initial ion concentration of 20ppm, tiO was added thereto 2 0.5g of powder, and stirred uniformly to obtain a reaction solution.
2) The silicone oil with the flow rate of 0.8mL/min is used as a carrier phase, and is mixed with the reaction liquid with the flow rate of 0.5mL/min in a micro-mixing unit to form a liquid column flow.
3) The liquid column flow enters the tubular reactor, the light source is received to carry out illumination and the photochemical reaction is carried out, and the residence time of the reaction liquid in the tubular reactor is 30min. Liquid-liquid phase separation is completed in a collecting bottle, and after sampling and adding a color reagent, analysis is carried out by an ultraviolet spectrophotometer, cr 6+ The conversion of ions was 43.4%.
Example 2:
the micro-mixing system with the reversed structure for the photochemical reaction in the tubular reactor in the embodiment 2 of the invention consists of a micro-mixing unit and a tubular photochemical reaction device, namely the micro-mixing unit and the tubular photochemical reaction device (comprising the tubular reactor and a light source).
The micro-mixing unit is of a cross-flow shearing type structure, the inner diameter of the main channel is 0.5mm, and the inner diameters of the two side channels are 1mm; the light source is a lamp band formed by a 50W LED lamp bead array, and the wavelength is 475nm; the tubular reactor is a perfluoroethylene propylene copolymer tube with an inner diameter of 1mm and an outer diameter of 2mm, and is wound in the manner of FIG. 4A; the light source lamp strip is arranged outside the tubular reactor, the light source lamp strip and the tubular reactor are coaxial, and the light source lamp strip and the tubular reactor are also in a spiral winding mode, and the distance between the control pipe wall and the LED lamp strip is 1cm (the outside of the tubular reactor which does not surround the axial center part is not wound with the LED lamp strip).
The step of degrading organic dye methyl orange by photochemical reaction by utilizing the micro-mixing system with the photochemical reaction in the tubular reactor with the reversing structure comprises the following steps:
1) 10mL of an aqueous solution having an initial concentration of 50ppm of methyl orange was prepared, and TiO was added thereto 2 40mg of powder was stirred uniformly to obtain a reaction solution.
2) Air with the flow rate of 0.2mL/min is used as a carrier phase, and is mixed with the reaction liquid with the flow rate of 0.5mL/min in a micro-mixing unit to form a liquid column flow.
3) The liquid column flow enters a tubular reactor with a reversing structure, is irradiated by a light source and undergoes a photoelectrochemical reaction, and the residence time of the reaction liquid in the tubular reactor is 15min. And collecting the liquid-solid mixture after the reaction by using a collecting bottle, realizing solid-liquid separation by centrifugation, analyzing the concentration of the methyl orange in the liquid by using an ultraviolet spectrophotometer, and calculating to obtain the conversion rate of the methyl orange to be 77.5%.
Example 3:
the micro-mixing system with the reversed structure for the photochemical reaction in the tubular reactor of the embodiment 3 of the invention consists of a micro-mixing unit and a 2-sleeve type photochemical reaction device (comprising 2 tubular reactors, 2 cold traps and 2 light sources).
The micro-mixing unit is of an improved coaxial ring pipe structure, the inner diameter of a liquid drop forming cavity is 2.5mm, the inner diameter of a reaction liquid channel is 1mm, the inner diameter d of an output channel is 1.5mm, and the inner pipe is a super-hydrophobic coating inner wall (the contact angle with dispersed phase liquid is 151 °); the first light source and the second light source are 100W high-pressure mercury lamps; the first cold trap and the second cold trap are made of high borosilicate glass, ultraviolet light below 300nm is filtered, and a mercury lamp is arranged in the cold traps; the tubular reactor is a perfluoroethylene propylene copolymer tube light source lamp with an inner diameter of 1mm and an outer diameter of 2mm, the outside of the tubular reactor, the first tubular reactor and the second tubular reactor are quartz glass tubes with an inner diameter of 2mm and an outer diameter of 3mm, and the tubular reactor is wound outside the cold trap in the mode of figure 4B.
The step of degrading organic dye methyl orange by photochemical reaction by utilizing the micro-mixing system with the photochemical reaction in the tubular reactor with the reversing structure comprises the following steps:
1) 10mL of an aqueous solution having an initial concentration of 50ppm of methyl orange was prepared, and TiO was added thereto 2 20mg of powder, and stirred uniformly to obtain a reaction solution.
2) The silicone oil with the flow rate of 0.4mL/min is used as a carrier phase and is mixed with the reaction liquid with the flow rate of 0.2mL/min in a micro-mixing unit to form a liquid column flow.
3) The liquid column flow enters a tubular reactor with a reversing structure, is irradiated by a light source and undergoes a photoelectrochemical reaction, and the residence time of the reaction liquid in the tubular reactor is 16min. And collecting the liquid-solid mixture after the reaction by using a collecting bottle, realizing solid-liquid separation by centrifugation, analyzing the concentration of the methyl orange in the liquid by using an ultraviolet spectrophotometer, and calculating to obtain the conversion rate of the methyl orange to be 79.2%.
Comparative example 1 (compare with example 1):
the present invention relates to a homogeneous-phase flow photo-chemical reaction in a tubular reactor of comparative example 1, which consists of a single tubular photochemical reaction device (comprising a tubular reactor and a light source). Comparative example 2 and example 1 differ in the winding manner of the tubular reactor and no carrier phase was introduced.
The tubular reactor is a perfluoroethylene propylene copolymer tube with the inner diameter of 1mm and the outer diameter of 2mm, and the tubular reactor is spirally wound around the axle center; the light source lamp strip is outside the tubular reactor, and the light source lamp strip and the tubular reactor are coaxial and also in a spiral winding mode (as shown in fig. 5), the distance between the tube wall and the LED lamp strip is controlled to be 1cm, and the residence time of the reaction liquid in the tubular reactor is ensured to be 30min as in the embodiment 1.
Degradation of Cr by photochemical reactions using the homogeneous flow in the tubular reactor described above 6+ The ion steps are as follows:
1) Preparation of Cr 6+ 10mL of an aqueous solution having an initial ion concentration of 20ppm, tiO was added thereto 2 0.5g of powder, and stirred uniformly to obtain a reaction solution.
2) The homogeneous flow reaction liquid with the flow rate of 1.3mL/min enters the tubular reactor, and is subjected to light source illumination to generate the photochemical reaction, and the residence time of the reaction liquid in the tubular reactor is 30min. Liquid-liquid phase separation is completed in a collecting bottle, and after sampling and adding a color reagent, analysis is carried out by an ultraviolet spectrophotometer, cr 6+ The conversion of ions was 29.0%, cr compared with example 1 6+ The conversion of ions was reduced by 33.1%.
Comparative example 2 (compare with example 1):
the micro-mixing system for photochemical reaction in the tubular reactor of the embodiment 2 of the invention consists of a micro-mixing unit and a tubular photochemical reaction device (comprising the tubular reactor and a light source). Comparative example 2 and example 1 differ in the manner of winding the tubular reactor.
The micro-mixing unit is of a T-shaped structure, the inner diameter of the main channel is 1mm, and the inner diameter of the side channel is 0.05mm; the light source is a lamp band formed by a 50W LED lamp bead array, and the wavelength is 475nm; the tubular reactor is a perfluoroethylene propylene copolymer tube with an inner diameter of 1mm and an outer diameter of 2mm, and is spirally wound around the axle center and has a structure (shown in figure 5) without extending out of the axle center part; the light source lamp strip is outside the tubular reactor, and the light source lamp strip and the tubular reactor are coaxial and also in a spiral winding mode, the distance between the tube wall and the LED lamp strip is controlled to be 1cm, and the residence time of the reaction liquid in the tubular reactor is ensured to be 30min as in the embodiment 1.
The micro-mixing system of photochemical reaction in the liquid column flow reinforced tubular reactor is utilized to carry out photochemical reaction to degrade Cr 6+ The ion steps are as follows:
1) Preparation of Cr 6+ 10mL of an aqueous solution having an initial ion concentration of 20ppm, tiO was added thereto 2 0.5g of powder, and stirred uniformly to obtain a reaction solution.
2) The silicone oil with the flow rate of 0.8mL/min is used as a carrier phase, and is mixed with the reaction liquid with the flow rate of 0.5mL/min in a micro-mixing unit to form a liquid column flow.
3) The liquid column flow enters the tubular reactor, the light source is received to carry out illumination and the photochemical reaction is carried out, and the residence time of the reaction liquid in the tubular reactor is 30min. Liquid-liquid phase separation is completed in a collecting bottle, and after sampling and adding a color reagent, analysis is carried out by an ultraviolet spectrophotometer, cr 6+ The conversion of ions was 39.4%, cr compared with example 1 6+ The conversion of ions was reduced by 9.2%.
Comparative example 3 (compare with example 2):
the micro-mixing system for photochemical reaction in the tubular reactor of comparative example 3 of the present invention consists of a micro-mixing unit and a tubular photochemical reaction device (comprising a tubular reactor and a light source). Comparative example 3 and example 2 differ in the manner of winding the tubular reactor.
The micro-mixing unit is of a cross-flow shearing type structure, the inner diameter of the main channel is 0.5mm, and the inner diameters of the two side channels are 1mm; the light source is a lamp band formed by a 50W LED lamp bead array, and the wavelength is 475nm; the tubular reactor is a perfluoroethylene propylene copolymer tube with an inner diameter of 1mm and an outer diameter of 2mm, and is wound in the manner shown in FIG. 5; the tubular reactor has no structure extending out of the axis part, the light source lamp strip is arranged outside the tubular reactor, the light source lamp strip and the tubular reactor are coaxial, the spiral winding mode is adopted, the distance between the tube wall and the LED lamp strip is controlled to be 1cm, and the residence time of the reaction liquid in the tubular reactor is ensured to be the same as that of the embodiment 7 and is 15min.
The step of degrading organic dye methyl orange by photochemical reaction by utilizing the micro-mixing system of photochemical reaction in the tubular reactor comprises the following steps:
1) 10mL of an aqueous solution having an initial concentration of 50ppm of methyl orange was prepared, and TiO was added thereto 2 40mg of powder was stirred uniformly to obtain a reaction solution.
2) Air with the flow rate of 0.2mL/min is used as a carrier phase, and is mixed with the reaction liquid with the flow rate of 0.5mL/min in a micro-mixing unit to form a liquid column flow.
3) The liquid column flow enters the tubular reactor, the light source is received to carry out illumination and the photochemical reaction is carried out, and the residence time of the reaction liquid in the tubular reactor is 15min. The liquid-solid mixture after the reaction was collected by a collection bottle, solid-liquid separation was achieved by centrifugation, and the concentration of methyl orange in the liquid was analyzed by an ultraviolet spectrophotometer, and the conversion rate of methyl orange was calculated to be 72.7%, which was 6.2% lower than that of example 2.
Comparative example 4 (compare with example 2):
the invention relates to a photochemical reaction in a tubular reactor with a reverse structure in comparative example 4, which consists of a tubular photochemical reaction device (comprising a tubular reactor and a light source). Comparative example 4 differs from example 2 in that no carrier phase was introduced.
The light source is a lamp band formed by a 50W LED lamp bead array, and the wavelength is 475nm; the tubular reactor is a perfluoroethylene propylene copolymer tube with an inner diameter of 1mm and an outer diameter of 2mm, and is wound in the manner of FIG. 4A; the light source lamp strip is arranged outside the tubular reactor, the light source lamp strip and the tubular reactor are coaxial, and the light source lamp strip and the tubular reactor are also in a spiral winding mode, and the distance between the control pipe wall and the LED lamp strip is 1cm (the outside of the tubular reactor which does not surround the axial center part is not wound with the LED lamp strip).
The step of degrading organic dye methyl orange by photochemical reaction in the tubular reactor with reverse structure comprises the following steps:
1) 10mL of an aqueous solution having an initial concentration of 50ppm of methyl orange was prepared, and TiO was added thereto 2 40mg of powder was stirred uniformly to obtain a reaction solution.
2) The aqueous solution of methyl orange is injected into the tubular reactor at the flow rate of 0.5mL/min, and the reaction solution is subjected to light source illumination to generate a photochemical reaction, wherein the residence time of the reaction solution in the tubular reactor is 15min. The liquid-solid mixture after the reaction was collected by a collection bottle, solid-liquid separation was achieved by centrifugation, and the concentration of methyl orange in the liquid was analyzed by an ultraviolet spectrophotometer, and the conversion rate of methyl orange was calculated to be 68.8%, which was 11.2% lower than that of example 2.
Comparative example 5 (compare with example 3):
the invention relates to a photochemical reaction in a tubular reactor of comparative example 5, which consists of a micro-mixing unit and a 2-sleeve photochemical reaction device (comprising 2 tubular reactors, 2 cold traps and 2 light sources). Comparative example 5 and example 3 differ in the manner of winding the tubular reactor.
The micro-mixing unit is of an improved coaxial ring pipe structure, the inner diameter of a liquid drop forming cavity is 2.5mm, the inner diameter of a reaction liquid channel is 1mm, the inner diameter d of an output channel is 1.5mm, and the inner pipe is a super-hydrophobic coating inner wall (the contact angle with dispersed phase liquid is 151 °); the first light source and the second light source are 100W high-pressure mercury lamps; the first cold trap and the second cold trap are made of high borosilicate glass, ultraviolet light below 300nm is filtered, and a mercury lamp is arranged in the cold traps; the tubular reactor is a perfluoroethylene propylene copolymer tube light source lamp with an inner diameter of 1mm and an outer diameter of 2mm, the outside of the tubular reactor, the first tubular reactor and the second tubular reactor are quartz glass tubes with an inner diameter of 2mm and an outer diameter of 3mm, and the two tubular reactors are wound outside the cold trap in the mode of figure 5.
The step of degrading organic dye methyl orange by photochemical reaction in the tubular reactor with reverse structure comprises the following steps:
1) 10mL of an aqueous solution having an initial concentration of 50ppm of methyl orange was prepared, and TiO was added thereto 2 20mg of powder, and stirred uniformly to obtain a reaction solution.
2) The silicone oil with the flow rate of 0.4mL/min is used as a carrier phase and is mixed with the reaction liquid with the flow rate of 0.2mL/min in a micro-mixing unit to form a liquid column flow.
3) The liquid column flow enters a tubular reactor with a reversing structure, is irradiated by a light source and undergoes a photoelectrochemical reaction, and the residence time of the reaction liquid in the tubular reactor is 16min. The liquid-solid mixture after the reaction was collected by a collection bottle, solid-liquid separation was achieved by centrifugation, and the concentration of methyl orange in the liquid was analyzed by an ultraviolet spectrophotometer, and the conversion rate of methyl orange was calculated to be 73.2%, which was 7.5% lower than that of example 3.
Comparative example 6 (comparison with example 3):
the invention of comparative example 6 adopts 1 set of stirring type photochemical reaction device, which consists of a light source and a cold trap, wherein the light source is placed in the cold trap, and the cold trap is placed in a stirring type reactor with a volume of 200 mL. Comparative example 6 differs from example 3 in that the reactor is stirred and no carrier phase is introduced.
The light source is a 1000W high-pressure mercury lamp (ensuring the consistent power of the unit volume of reaction liquid), the cold trap is made of borosilicate glass, and ultraviolet light below 300nm is filtered.
The step of degrading methyl orange by utilizing the stirring type photochemical reaction device for photochemical reaction comprises the following steps:
1) 100mL of an aqueous solution having an initial concentration of 50ppm of methyl orange was prepared, and TiO was added thereto 2 200mg of powder was stirred uniformly to obtain a reaction solution.
2) Placing the reaction solution into a stirring reactor corresponding to a cold trap, starting a light source to initiate photochemical reaction for 16 minutes, collecting the liquid-solid mixture after the reaction by using a collecting bottle, centrifuging to realize solid-liquid separation, analyzing the concentration of methyl orange in the liquid by using an ultraviolet spectrophotometer, and calculating to obtain the conversion rate of the methyl orange of 58.0 percent, compared with the conversion rate of the methyl orange
Example 3, the conversion of methyl orange was reduced by 26.7%.
While the invention has been described in detail in the general context and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (9)
1. A micro-mixing system for photochemical reactions in a tubular reactor, characterized in that the system comprises a micro-mixing unit and a tubular photochemical reaction device, wherein the liquid-liquid micro-mixing unit is connected in series with the tubular photochemical reaction device, and in the liquid-liquid micro-mixing unit, a liquid or gaseous carrier phase which is not compatible with a reaction liquid shears the reaction liquid into liquid columns or liquid drops, and the tubular photochemical reaction device comprises a tubular reactor, a light source and a cold trap; the tubular reactor has 1 or more than 1 turning structures different from the winding direction of the light source; the turning structure comprises a reversing structure or a strengthening mixing structure, wherein the reversing structure means that a tubular reactor is added with a turning angle of more than 30 degrees in the spiral winding process, and the specific arrangement mode is that a supporting structure is arranged on the outer side of a light source main body, and the tubular reactor is wound on the supporting structure and returns to the light source main body after being wound out of the light source main body; the reinforced mixing structure is a branch structure which is added on the main body of the light source in a stage and forms a certain angle with the axial direction of the main body of the light source, the branch structure is used as a part of the light source, the tubular reactor is spirally wound on the branch structure, and the absolute value of the certain angle is larger than 30 degrees; the micro-mixing unit comprises a micro-channel device, wherein the micro-channel device comprises a reaction liquid channel, a carrier phase fluid channel, a liquid drop forming cavity and an output pipeline, one end of the reaction liquid channel and one end of the carrier phase fluid channel are inlets of reaction liquid or carrier phase fluid, the other end of the reaction liquid channel and the carrier phase fluid are communicated in the liquid drop forming cavity, the reaction liquid and the carrier phase fluid are subjected to intersection shearing mixing in the liquid drop forming cavity to form a liquid column flow, and the liquid column flow flows from the liquid drop forming cavity to the rear output pipeline; the output pipeline is connected with the tubular photochemical reaction device.
2. The micro-hybrid system according to claim 1, wherein: the micro-mixing unit is a T-shaped, Y-shaped, cross-flow shearing type, hydrodynamic focusing type, coaxial annular pipe type or coaxial annular pipe improved microchannel device.
3. The micro-hybrid system according to claim 1, wherein: the tubular photochemical reaction device adopts a light-transmitting tubular reactor, and the number of light sources and the length of the tubular reactor are determined according to the illumination time required by photochemical reaction.
4. A micro-mixing system according to any one of claims 1-3, characterized in that: the micro-mixing unit equipment is made of polymer, stainless steel, inorganic glass or a mixture of the above materials, and the channel size is 0.05-50 mm.
5. A micro-mixing system according to any one of claims 1-3, characterized in that: the tubular reactor is made of perfluoroethylene propylene copolymer, polytetrafluoroethylene, quartz glass, silicate glass, high borosilicate glass or the mixture thereof, and the inner diameter of the tubular reactor is 0.05-50 mm.
6. The micro-hybrid system according to claim 1, wherein: the light source in the tubular photochemical reaction device is a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a light-emitting diode lamp or a combination of the high-pressure mercury lamp and the low-pressure mercury lamp, and the light emitted by the light source is ultraviolet light, visible light, infrared light or a combination of the ultraviolet light, the visible light, the infrared light and the combination of the ultraviolet light and the infrared light; the cold trap is made of quartz glass, silicate glass, high borosilicate glass or a mixture of the quartz glass, the silicate glass and the high borosilicate glass.
7. A method of photochemical reactions in a tubular reactor, characterized in that it is carried out with a micro-mixing system according to any of claims 1-6, comprising the steps of:
(1) In the micro-mixing unit, liquid or gas which is not mutually soluble with photochemical reaction liquid is used as carrier phase fluid, and the liquid column fluid is obtained by adjusting the flow rate of two phases and shearing the liquid phase fluid into a liquid column;
(2) The obtained liquid column flow enters a tubular reactor to receive illumination, the illumination reaction is carried out in the liquid column of the reaction liquid, and the reaction liquid always keeps the liquid column type flowing in the illumination process;
(3) The liquid column flow passes through the tubular reactor once or circulates for many times, the total residence time is controlled according to the reaction progress, and the product solution is obtained after phase separation.
8. The method of claim 7, wherein the reaction solution is a solution containing a photochemical reaction component.
9. The method of claim 7, wherein the flow ratio of the carrier phase to the reaction liquid phase is 1: 20-20: 1, a step of; the carrier phase comprises: electrolyte solution, silicone oil, alkane liquid, or nitrogen and argon inert gas.
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| CN111434377B (en) * | 2019-01-11 | 2022-07-15 | 中国石油化工股份有限公司 | Coil microreactor and microreactor system |
| CN109806823A (en) * | 2019-03-14 | 2019-05-28 | 凯莱英医药集团（天津）股份有限公司 | Continuous photochemical reaction unit and system |
| CN111790335A (en) * | 2019-04-08 | 2020-10-20 | 上海交通大学 | Ultraviolet photochemical reactor device based on continuous flow technology |
| CN111482154A (en) * | 2020-05-18 | 2020-08-04 | 嘉兴孚诺纳米科技有限公司 | Two-channel efficient continuous flow photochemical mixing device and mixing method thereof |
| CN113975227A (en) * | 2020-07-10 | 2022-01-28 | 天津大学 | Flow type synthesis device and synthesis method of nanogel |
| CN113877494A (en) * | 2021-09-29 | 2022-01-04 | 国家纳米科学中心 | Multifunctional flowing microtube reaction device and operation method |
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