CN115646383A - Microreactor with controllable reaction process and preparation method thereof - Google Patents

Microreactor with controllable reaction process and preparation method thereof Download PDF

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Publication number
CN115646383A
CN115646383A CN202211199952.1A CN202211199952A CN115646383A CN 115646383 A CN115646383 A CN 115646383A CN 202211199952 A CN202211199952 A CN 202211199952A CN 115646383 A CN115646383 A CN 115646383A
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flow channel
reaction
layer
microreactor
channel
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CN202211199952.1A
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周伟
林伟铭
周姝判
褚旭阳
李新颖
钟雨晨
吴粦静
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Xiamen University
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Xiamen University
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Abstract

The invention discloses a microreactor with a controllable reaction process, which comprises a fluid channel layer and a sealing layer, wherein the surface of the fluid channel layer is provided with a reaction flow channel, a junction region and at least two feeding flow channels, and the junction region is arranged at the junction of the tail ends of the at least two feeding flow channels and the starting end of the reaction flow channel; the sealing layer is covered and bonded on the fluid channel layer, and is provided with a sealing inlet which is correspondingly communicated with the starting end of each feeding flow channel and a sealing outlet which is correspondingly communicated with the tail end of the reaction flow channel; the fluid channel layer and the sealing layer are made of flexible materials, and the cross section of the reaction flow channel is changed when the microreactor is bent so as to influence the reaction process. The invention also discloses a preparation method of the composition. The cross section of the channel can be changed along with the macroscopic deformation of the microreactor, the reaction process can be regulated and controlled in real time, and the controllability of the reaction is improved; the method is suitable for the mixed reaction requirements of reactants with different flow rates and different viscosities.

Description

Microreactor with controllable reaction process and preparation method thereof
Technical Field
The invention belongs to the technical field of microreactors, and particularly relates to a microreactor with a controllable reaction process and a preparation method thereof.
Background
The microreactor technology is widely applied to various fields such as biological analysis, medical diagnosis, chemical synthesis and the like, and takes a microstructure unit as a core to perform chemical reaction in a micron or submicron limited space. By reducing the dispersion scale of the system and strengthening mixing and transfer, the method has the advantages of high-efficiency mixing capability, good mass and heat transfer characteristics, highly controllable reaction process and the like.
Microreactors can be divided into two types, static and dynamic. The static microreactor is widely used, does not need external energy input, mainly utilizes the geometric structure shape of the reactor to increase the contact area of fluid, promotes the uniform mixing of the fluid and fully reacts, and is mainly represented by an obstacle type and a flow channel structure type. The dynamic micro-reactor promotes disturbance of fluid by an external energy field, destroys a laminar flow state, promotes chaotic convection, and is mainly represented by pressure driving and sound field driving.
The patent provides a micro-reaction channel structure and a micro-reactor based on the same, the inner wall of the micro-channel or the middle of the micro-channel is provided with a certain number of spine structures, the spines are as petals in a flower, the roots are gathered together mutually, the leaf tips are unfolded along the circumferential direction, the spines gathered together at the roots form a micro-structure, and the micro-reaction channel structure is combined with piezoelectric ceramics as an active energy module to generate high-frequency vibration turbulence. The method solves the defects of long reaction distance, poor operability and the like of the existing microreactor.
The patent proposes a combined baffle type microreactor which is composed of microreaction chambers arranged in an array on opposite surfaces of an upper microreactor substrate and a lower microreactor substrate, microchannels sequentially communicated with the microreaction chambers, a liquid inlet channel and a liquid outlet channel; the micro-reaction chamber is in an oval shape, and a plurality of groups of baffles for folding the fluid are arranged in the flowing direction of the fluid; the outer diameter of the micro-channel is provided with a wave junction structure capable of forming fluid turbulence, so that fluid is repeatedly folded and collided, and the mixing effect of the fluid is effectively improved.
Although some of the existing microreactors already have a certain degree of intensified mixing, these microreactors have the following disadvantages: 1. the controllability is poor, and the reaction control can be generally carried out only by adjusting the flow rate; 2. the structure is fixed, and the mixing reaction requirements of reactants with different flow rates and different viscosities cannot be met.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a microreactor with a controllable reaction process and a preparation method thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a microreactor with a controllable reaction process comprises a fluid channel layer and a sealing layer, wherein a reaction flow channel, a junction region and at least two feeding flow channels are formed in the surface of the fluid channel layer, and the junction region is arranged at the junction of the tail ends of the at least two feeding flow channels and the starting end of the reaction flow channel; the sealing layer is covered and bonded on the fluid channel layer, and is provided with a sealing inlet which is correspondingly communicated with the starting end of each feeding flow channel and a sealing outlet which is correspondingly communicated with the tail end of the reaction flow channel; the fluid channel layer and the sealing layer are made of flexible materials, and the cross section of the reaction flow channel is changed when the microreactor is bent so as to influence the reaction process.
When external force is applied to bend the microreactor, the wall surfaces of the reaction flow channel are close to each other due to deformation, and the width and the cross section of the reaction flow channel are reduced, so that the control of reaction can be realized.
Optionally, the fluid channel layer is further provided with a flow channel inlet at the beginning end of each feeding flow channel, and the flow channel inlet is in matched conduction with the corresponding sealing inlet; the fluid channel layer is also provided with a reaction flow channel outlet at the tail end of the reaction flow channel, and the reaction flow channel outlet is matched and communicated with the sealed outlet.
Optionally, the reaction flow channel extends in a zigzag manner along a first direction of the fluid channel layer, and a width of the reaction flow channel in the first direction changes when the microreactor is bent.
Optionally, the reaction flow channel is alternately connected by a longitudinal section parallel to the first direction and a transverse section perpendicular to the first direction to perform the zigzag extension.
Optionally, the material of the fluid channel layer and the sealing layer is a PDMS thin film material, wherein the thickness of the fluid channel layer is 1-3mm, and the depths of the plurality of feeding flow channels, the reaction flow channels and the junction region are 200-900 μm.
Optionally, the width of the reaction flow channel is 3-20 μm when the reaction flow channel is not stressed, and the width variation amplitude when the reaction flow channel is bent is 50-80%.
The fluid channel layer and the sealing layer are made of PDMS thin film materials in the same batch, and the depths of the feeding flow channel, the reaction flow channel and the confluence area are equal.
A preparation method of the microreactor with the controllable reaction process comprises the following steps:
step 1): mixing a PDMS material with a curing agent to prepare a PDMS solution;
step 2): pouring the PDMS solution on a substrate, removing bubbles in the PDMS solution, and heating and curing to obtain a PDMS film;
step 3): peeling off the PDMS film obtained in the step 2) from the substrate, processing a fluid channel, a confluence area, a reaction channel and an inlet and an outlet by using ultraviolet laser, and then cutting the film to obtain a fluid channel layer and a sealing layer;
step 4): and bonding the fluid channel layer and the sealing layer to enable the feeding flow channel, the reaction flow channel and the confluence region to be enclosed with the sealing layer to form a flow channel cavity.
Optionally, in step 1), the mixing ratio of the PDMS material to the curing agent ranges from 10; in the step 2), the heating curing is carried out for 6-8h at 50-75 ℃.
Optionally, the laser power range of the ultraviolet laser processing in the step 3) is 5.8-8.8kw.
Optionally, the fluid channel layer and the sealing layer in the step 4) are placed in a bonding machine, and oxygen plasma treatment is carried out for 45-60 seconds to carry out aligned bonding.
The width ranges of the feeding flow channel and the reaction flow channel are 3-20 mu m, the diameter range of the confluence area is 0.5-1.5mm, the aperture range of the inlet and the outlet is 0.8-1.5mm, and the depth range of the flow channel is 200-900 mu m. The inlet and the outlet refer to a flow channel inlet and a sealed inlet, and a flow channel outlet and a sealed outlet.
The invention has the beneficial effects that:
1. compared with the prior micro-reactor, the adjustable flow channel section is added, and the reaction process is further controllable on the basis that only the input flow can be adjusted originally;
2. compared with the prior microreactor with a fixed channel structure, the microreactor has the advantages that the channel structure is controllable, the requirements of mixing reaction of reactants with different flow rates can be met, and the microreactor is not easy to block;
3. compared with the existing micro-reactor processing mode, the invention uses ultraviolet laser to process without a die and photoetching, greatly simplifies the process and greatly reduces the processing difficulty of the micro-reactor.
Drawings
FIG. 1 is an exploded schematic view of a microreactor with controllable reaction processes according to an embodiment of the present invention;
FIG. 2 is a schematic top view of a fluid channel layer according to an embodiment of the invention;
FIG. 3 is a schematic top view of a sealing layer according to an embodiment of the invention;
FIG. 4 is a schematic top view of a fluid channel layer in a post-bending state according to an embodiment of the invention;
FIG. 5 is a schematic front view of a fluid channel layer in a post-bending state according to an embodiment of the invention;
FIG. 6 is a top view of a reaction flow channel region according to an embodiment of the invention;
FIG. 7 is a top view of a post-bending state of a reaction flow channel region according to an embodiment of the invention;
fig. 8 is a flow chart of a method for manufacturing a microreactor with controllable reaction processes according to an embodiment of the present invention.
Detailed Description
The invention is further explained below with reference to the figures and the specific embodiments. The drawings are only schematic and can be easily understood, and the specific proportion can be adjusted according to design requirements. The above and below relationships and the front/back definitions of the relative elements in the drawings described herein are understood to refer to the relative positions of the elements, and therefore, the elements may be turned over to present the same elements, all within the scope of the present disclosure.
The beginning and the end are defined herein in terms of the direction of fluid flow in the flow channel, i.e. the fluid flows from the beginning to the end.
Referring to fig. 1 to 3, a microreactor in which a reaction process is controlled according to an embodiment includes a fluid channel layer 100 and a sealing layer 200, the fluid channel layer 100 is provided with a first feeding flow channel 111, a second feeding flow channel 131, a reaction flow channel 121, and a junction region 140, and the junction region 140 is provided at an intersection of a terminal end of the first feeding flow channel 111, a terminal end of the second feeding flow channel 131, and a starting end of the reaction flow channel 121. The fluid channel layer 100 is further provided with a first feeding flow channel inlet 110, a second feeding flow channel inlet 130 and a reaction flow channel outlet 120, the first feeding flow channel inlet 110 is communicated with the beginning of the first feeding flow channel 111, the second feeding flow channel inlet 130 is communicated with the beginning of the second feeding flow channel 131, and the reaction flow channel outlet 120 is communicated with the end of the reaction flow channel 121.
Referring to fig. 1 and 3, the sealing layer 200 is provided with a first sealing inlet 210, a second sealing inlet 230 and a sealing outlet 220, which are respectively corresponding to the first feeding channel inlet 110, the second feeding channel inlet 130 and the reaction channel outlet 120. The sealing layer 200 covers the fluid channel layer 100, and the fluid channel layer 100 is bonded to the sealing layer 200, so that the first feeding channel 111, the second feeding channel 131, the reaction channel 121, and the junction region 140 and the bottom surface of the sealing layer 200 are sealed and enclosed to form a channel cavity.
The fluid passage layer 100 and the sealing layer 200 are formed using a bendable flexible material. The two side wall surfaces of the reaction flow channel 121 area are gradually close to each other under the influence of the whole bending deformation of the microreactor, the width of the reaction flow channel 121 and the cross section of the flow channel are reduced, and the reaction process and the reaction effect are influenced. In the present embodiment, referring to fig. 2 and fig. 4 to fig. 7, the reaction flow channel 121 extends zigzag in a first direction of the fluid channel layer 100, the first and second feeding flow channels 111 and 131 extend in a direction perpendicular to the first direction, and when the microreactor is bent in the direction perpendicular to the first direction, the flow channel width of the reaction flow channel 121 in the first direction changes when the microreactor is bent. The first direction mentioned here refers to any direction of the surface of the fluid passage layer. Specifically, the reaction flow channel 121 is formed by alternately connecting a longitudinal section parallel to the first direction and a transverse section perpendicular to the first direction for zigzag extension, the cross sections of the longitudinal section and the transverse section are alternately changed, the total length of the flow channel is increased, and the mixing reaction is facilitated. Referring to fig. 5, when the reaction channel is bent in a direction perpendicular to the first direction, the wall surfaces of the reaction channel are deformed to approach each other, the width of the reaction channel and the cross-section of the reaction channel are reduced, and the width of the reaction channel in the longitudinal section is reduced, thereby controlling the reaction.
The width of the reaction flow channel is 3-20 μm when the reaction flow channel is not stressed, and the width variation amplitude is 50-80% when the reaction flow channel is bent.
The fluid channel layer 100 and the sealing layer 200 are made of PDMS film material in the same batch. The first feed channel 111, the second feed channel 131, the reaction channel 121, and the confluence region 140 have the same depth. The width of the reaction flow channel 121 is determined according to the flow channel width range in which the bending angle of the microreactor can be adjusted.
Referring to fig. 8, the method for preparing a microreactor with controllable reaction process comprises:
step 1: weighing 6g of PDMS and 0.6g of curing agent 10 according to the proportion of 1, and fully stirring and mixing to prepare a PDMS solution; an example of a curing agent is SYLGARD 184, although other conventional curing agents may be used.
Step 2: pouring the PDMS solution on a silicon chip, placing the silicon chip on a vacuum drying oven, maintaining the pressure for 0.5h at-0.1 MPa, removing bubbles, and placing the silicon chip on a drying oven, and drying the silicon chip for 6h at 55 ℃ to obtain a PDMS film with the thickness of 1.5 mm;
and step 3: processing a fluid channel, a junction region 140 and an inlet and an outlet by using ultraviolet laser with the laser power of 7Kw, and cutting and taking down the fluid channel layer 100 and the sealing layer 200, wherein the thickness of the fluid channel layer 100 is 1.5mm, and the depth of a flow channel is 345 microns; placing the fluid channel layer 100 and the sealing layer 200 in an ultrasonic cleaning machine for cleaning for 3-5min, and drying in an oven for 3-5min;
and 4, step 4: the treated fluid channel layer 100 and the sealing layer 200 were placed in a bonder and oxygen plasma treated for 45s to align the bond.
During manufacturing, the width of the first feeding flow channel 111, the width of the second feeding flow channel 131 and the width of the reaction flow channel 121 are within the range of 3-20 μm, the diameter of the confluence region 140 is within the range of 0.5-1.5mm, the aperture of the inlet and the outlet (the first sealing inlet 210, the second sealing inlet 230, the sealing outlet 220, the first feeding flow channel inlet 110, the second feeding flow channel inlet 130 and the reaction flow channel outlet 120) is within the range of 0.8-1.5mm, and the depth of the flow channel is within the range of 200-900 μm.
The invention is applicable to, but not limited to, fluid dynamics control in a microreactor, including flow control and flow resistance regulation; and opening and closing the flow channel. The application occasions comprise: preparation of nanoparticles, fine chemical synthesis, etc.
In one embodiment, sulfur composite nanoparticles can be synthesized using a microreactor with a controlled reaction process as described in the present invention. Under the driving of the syringe pump, a mixture containing HCl, PVP, and deionized water is injected into the first feeding flow channel 111, and a mixture containing sodium thiosulfate and deionized water is injected into the second feeding flow channel 131, both of which are injected at different flow rates. And (3) collecting the generated solution in a centrifuge cup, centrifuging in a high-speed centrifuge, pouring out supernatant, and performing vacuum drying to obtain the S @ PVP nano particles. The different bending angles of the reactor are adjusted, the width of the micro-channel is changed, the mixing diffusion degree of reactants is adjusted, and the mixing path required by complete mixing is reduced, so that the controllable preparation of the S @ PVP nano particles with the particle size of 248-785 nm is realized, and the nano-particles can be used as the cathode material of a lithium-sulfur battery.
The above examples are only used to further illustrate a microreactor with controllable reaction process and a method for preparing the same according to the present invention, but the present invention is not limited to the examples, and any simple modifications, equivalent changes and modifications made to the above examples according to the technical spirit of the present invention fall within the scope of the technical solution of the present invention.

Claims (10)

1. A microreactor with controllable reaction process is characterized in that: the device comprises a fluid channel layer and a sealing layer, wherein a reaction flow channel, a junction area and at least two feeding flow channels are formed in the surface of the fluid channel layer, and the junction area is arranged at the intersection of the tail ends of the at least two feeding flow channels and the initial end of the reaction flow channel; the sealing layer is covered and bonded on the fluid channel layer, and is provided with a sealing inlet which is correspondingly communicated with the starting end of each feeding flow channel and a sealing outlet which is correspondingly communicated with the tail end of the reaction flow channel; the fluid channel layer and the sealing layer are made of flexible materials, and the cross section of the reaction flow channel is changed when the microreactor is bent so as to influence the reaction process.
2. The microreactor of claim 1, wherein the reaction process is controllable by: the fluid channel layer is also provided with a flow channel inlet at the starting end of each feeding flow channel, and the flow channel inlets are matched and communicated with the corresponding sealing inlets; the fluid channel layer is also provided with a reaction flow channel outlet at the tail end of the reaction flow channel, and the reaction flow channel outlet is matched and communicated with the sealed outlet.
3. The microreactor of claim 1, wherein the reaction process is controllable by: the reaction flow channel extends along a first direction of the fluid channel layer in a zigzag manner, and the width of the flow channel in the first direction changes when the microreactor is bent.
4. A microreactor controlled according to reaction process of claim 3, wherein: the reaction flow channel is alternately connected by a longitudinal section parallel to the first direction and a transverse section vertical to the first direction to perform the zigzag extension.
5. The microreactor of claim 1, wherein the reaction process is controllable by: the material of the fluid channel layer and the sealing layer is PDMS film material, wherein the thickness of the fluid channel layer is 1-3mm, and the depths of the plurality of feeding flow channels, the plurality of reaction flow channels and the plurality of confluence areas are 200-900 μm.
6. The microreactor of claim 1, wherein the reaction process is controllable by: the width of the reaction flow channel is 3-20 μm when the reaction flow channel is not stressed, and the width variation amplitude is 50-80% when the reaction flow channel is bent.
7. A method for preparing a microreactor having a controllable reaction process according to any one of claims 1 to 6, comprising:
step 1): mixing a PDMS material with a curing agent to prepare a PDMS solution;
step 2): pouring the PDMS solution on a substrate, removing bubbles in the PDMS solution, and heating and curing to obtain a PDMS film;
step 3): peeling off the PDMS film obtained in the step 2) from the substrate, processing a fluid channel, a confluence area, a reaction channel and an inlet and an outlet by using ultraviolet laser, and then cutting the film to obtain a fluid channel layer and a sealing layer;
step 4): and bonding the fluid channel layer and the sealing layer to enable the feeding flow channel, the reaction flow channel and the confluence region to be enclosed with the sealing layer to form a flow channel cavity.
8. The method of claim 7, wherein: in the step 1), the mixing ratio of the PDMS material to the curing agent is in the range of 10 to 25; in the step 2), the heating curing is carried out for 6-8h at 50-75 ℃.
9. The method of claim 7, wherein: the laser power range of the ultraviolet laser processing in the step 3) is 5.8-8.8kw.
10. The method of claim 7, wherein: and 4) placing the fluid channel layer and the sealing layer in a bonding machine in the step 4), and carrying out oxygen plasma treatment for 45-60s to carry out aligned bonding.
CN202211199952.1A 2022-09-29 2022-09-29 Microreactor with controllable reaction process and preparation method thereof Pending CN115646383A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1460036A (en) * 2000-09-22 2003-12-03 财团法人川村理化学研究所 Very small chemical device and flow rate adjusting method thereof
CN102745660A (en) * 2011-04-18 2012-10-24 中国科学院大连化学物理研究所 Microfluidic chip based method for synthesizing needle-like hydroxyapatite nanoparticle
CN208177428U (en) * 2018-01-02 2018-12-04 山东省科学院能源研究所 A kind of micro passage reaction
CN114534809A (en) * 2022-02-25 2022-05-27 河海大学常州校区 Microfluidic particle control device with adjustable cross section shape and particle control method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1460036A (en) * 2000-09-22 2003-12-03 财团法人川村理化学研究所 Very small chemical device and flow rate adjusting method thereof
CN102745660A (en) * 2011-04-18 2012-10-24 中国科学院大连化学物理研究所 Microfluidic chip based method for synthesizing needle-like hydroxyapatite nanoparticle
CN208177428U (en) * 2018-01-02 2018-12-04 山东省科学院能源研究所 A kind of micro passage reaction
CN114534809A (en) * 2022-02-25 2022-05-27 河海大学常州校区 Microfluidic particle control device with adjustable cross section shape and particle control method

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