CN113828260B - Manufacturing method and application of ceramic microreactor - Google Patents
Manufacturing method and application of ceramic microreactor Download PDFInfo
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- CN113828260B CN113828260B CN202111289912.1A CN202111289912A CN113828260B CN 113828260 B CN113828260 B CN 113828260B CN 202111289912 A CN202111289912 A CN 202111289912A CN 113828260 B CN113828260 B CN 113828260B
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00011—Laboratory-scale plants
- B01J2219/00013—Miniplants
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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
- B01J2219/00819—Materials of construction
- B01J2219/00824—Ceramic
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The preparation method comprises the preparation of ceramic base materials, the preparation of a ceramic substrate containing micro-channels, the loading of catalysts by the micro-channels and the encapsulation and molding of the ceramic microreactor. The ceramic microreactor manufactured by the invention is used for photochemical reaction, the manufacturing process is simple, the packaging cost is low, and the packaged microreactor has good light transmittance, sealing performance and durability; then the catalyst is loaded on the rough surface of the ceramic and the micro-channel is transparently packaged, the catalyst wall-hanging ceramic micro-reactor is utilized to improve the efficiency of photodegradation of organic matters in the water body, and the photodegradation reaction is carried out by the method, so that the method has the advantages of short reaction residence time, continuous reaction, no need of recycling the catalyst and long-term and effective effect.
Description
Technical Field
The invention belongs to the technical field of microreactors, and particularly relates to a manufacturing method and application of a ceramic microreactor.
Background
With the rapid development of economy, the problem of water pollution is increasingly serious. Restoration of water pollution produced by industry, agriculture and life has attracted attention from all parties. Wherein the organic wastewater produced by industrial production has large toxicity, high chromaticity, large pH value change and serious environmental pollution. Photocatalytic oxidation of organic wastewater with photocatalysts is considered a relatively inexpensive and efficient method. The photocatalysis water treatment technology is an environment-friendly chemical treatment method, and can use a small amount of catalyst in a short time to efficiently treat pollution of organic matters to water; however, the conventional reactor is used for photodegradation treatment, the problems of difficult catalyst recovery, secondary pollution to equipment, low intermittent reaction efficiency and the like are solved, the problems of low light energy utilization rate, photon transfer limitation, lack of reaction paths due to lack of oxygen deficiency and the like are solved, the advantages of high mass transfer efficiency, short diffusion time, controllable reaction paths and the like of the microreactor are provided for the microreactor, meanwhile, the rough surface and certain porosity of the ceramic material are convenient for loading the catalyst, and the acid and alkali resistance of the ceramic material enables the ceramic material to be applied to a harsh reaction environment, so that the ceramic microreactor is considered to be applied to photodegradation reaction. At first glance, the micro-reaction technology and water treatment appear to be contradictory, as the former is designed to handle small amounts of solution, while the latter requires large amounts of production. This mismatch can be compensated for by expanding the microreactor.
Although the photocatalysis water treatment technology is an environment-friendly chemical treatment method, the problems of low light energy utilization rate, photon transfer limitation, lack of reaction paths due to lack of oxygen deficiency and the like exist, and the advantages of high mass transfer efficiency, short diffusion time, controllable reaction paths and the like of the microreactor provide a feasible solution, meanwhile, the rough surface and certain porosity of the ceramic material facilitate the loading of the catalyst, and the acid and alkali resistance of the ceramic material enables the ceramic material to be applied to harsh reaction environments, so that the ceramic microreactor is considered to be applied to photodegradation reaction. At present, the micro-machining of the ceramic material is complex, after the micro-channel is machined by the ceramic material, the sealing difficulty of the micro-channel is high, the micro-channel is easy to collapse in the sintering process, the isostatic pressing integrated sintering is used, the equipment and the process are complex, and the cost is high; the gasket with high strength is used for pressing and sealing, so that the weather resistance is poor; the ceramic micro-channel packaging mode directly influences the performance of the ceramic micro-reactor due to the fact that the adhesive is poor in high temperature resistance and solvent resistance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a manufacturing method and application of a ceramic microreactor.
The invention is realized by the following technical scheme.
The invention provides a manufacturing method of a ceramic microreactor, which comprises the following steps:
preparing a ceramic substrate material:
mixing 75-85 parts of alumina powder, 15-25 parts of cordierite powder, 2-6 parts of titanium dioxide and 1-2 parts of methylcellulose powder according to parts by weight, ball milling, sieving, adding water, ethanol and propanol, performing vacuum pugging, and aging to obtain a ceramic substrate material;
step two, manufacturing a ceramic substrate containing micro channels:
putting the ceramic substrate material obtained in the previous step into a mould for compression molding to manufacture a ceramic green body, drying the ceramic green body at 70-100 ℃ after demoulding, polishing the ceramic green body to be smooth by using sand paper after the ceramic green body is dried, machining the micro-channel on the ceramic green body, and then placing the machined ceramic green body into a high-temperature furnace for sintering, wherein the sintering process is as follows: firstly, heating to 350-450 ℃ at a heating rate of 4-6 ℃/min, and then preserving heat for 25-35min to perform glue discharging on the ceramic green embryo; then heating to 950-1050 ℃ at a heating rate of 3-5 ℃/min, and preserving heat for 25-35min to perform pre-sintering of the ceramic green body; then heating to 1300-1450 ℃ at a heating rate of 3-5 ℃/min, preserving heat for 0.5-1.5h, sintering the ceramic green body, and naturally cooling after the sintering is completed to obtain the ceramic substrate containing the micro-channels;
step three, a micro-channel carries a catalyst, and packaging and forming of a ceramic micro-reactor:
preparing a photodegradation catalyst into a suspension, dripping the suspension into a micro-channel loaded on the ceramic substrate obtained in the previous step, drying at 70-90 ℃, and repeating for 2-4 times; filling molten liquid paraffin into a micro-channel dropwise added on a ceramic substrate of suspension, covering resin on the surface of the ceramic substrate filled with paraffin, curing at 15-25 ℃ for 16-36h, placing the ceramic substrate covered with resin into a baking oven at 40-90 ℃ for heating and curing for 3-6h, heating to 50-90 ℃ after curing is finished, removing the filler in the micro-channel, and cleaning and drying after the filler volatilizes to obtain the ceramic microreactor.
In the first step, the alumina powder and the cordierite powder are industrial grade, the titanium dioxide is of analytical grade, and the viscosity of the methylcellulose is 40000 MPa.s; in the mixing, 80 parts of alumina powder, 20 parts of cordierite powder, 4 parts of titanium dioxide and 1.5 parts of methylcellulose powder are mixed according to parts by weight; ball milling was performed for 4 hours, followed by sieving with a 3000 mesh screen.
Further, in the second step, the prepared ceramic green body is round, and has a diameter of 60mm and a thickness of 3-13mm; and (3) polishing the dried ceramic green blank by using 150-mesh sand paper, and then polishing the ceramic green blank by using 2000-mesh sand paper.
Further, in the second step, when the micro-channel is machined by using a machining method, a cutter with the diameter of phi of 0.2mm-1mm is used, the wall thickness of the machined micro-channel is more than 4mm, and a volatile pore canal of the filling material needs to be reserved, and the diameter of an overflow pore canal is 0.5-2.5mm.
Further, in the second step, the process of sintering the processed ceramic green body in a high temperature furnace comprises the following steps: firstly, heating to 400 ℃ at a heating rate of 5 ℃/min, and then preserving heat for 30min to perform glue discharging on the ceramic green body; then heating to 1000 ℃ at a heating rate of 4 ℃/min, and then preserving heat for 30min to perform pre-sintering of the ceramic green body; then heating to 1300-1450 ℃ at a heating rate of 4 ℃/min, preserving heat for 1h, sintering the ceramic green body, and naturally cooling to obtain the ceramic substrate containing the micro-channels.
Further, the micro-channel processed in the second step is a serpentine channel with the width of 0.5mm, the height of 0.8mm and the length of 20-60 mm.
In the third step, the photodegradation catalyst, water, isopropanol and polyvinyl alcohol are mixed and stirred to prepare a suspension, the suspension is dripped into a micro-channel loaded on a ceramic substrate, and the suspension is dried at 80 ℃ and repeated for 3 times.
Further, in the third step, the resin is covered on the surface of the ceramic substrate after filling, and then the ceramic substrate is cured for 24 hours at 20 ℃, then the ceramic substrate is put into a 60 ℃ oven for heating and curing for 4 hours, and the ceramic substrate is heated to 70 ℃ after curing to remove the filling substances in the micro-channels.
The ceramic microreactor prepared by the method for manufacturing the ceramic microreactor according to any one of the above steps uses a liquid phase reaction system, injects liquid phase reactants into the ceramic microreactor through a microfluidic pump, and photo-degrades a catalyst under illumination to generate free radical oxidation degradation organic matters.
Further, the micro-flow pump is a micro-flow peristaltic pump, and the flow rate of the liquid phase is 20-200 mu L/min; the reaction residence time of the liquid phase reactant in the ceramic micro-reactor is 1-20min, and the pressure of the ceramic micro-reactor is controlled below 3bar when the reaction is carried out.
The invention has the beneficial effects that: 1. the invention protects the shape of the micro-channel by means of low boiling point paraffin, and the high-permeability resin is solidified and packaged to form the ceramic micro-reactor with the transparent window, the ceramic micro-reactor manufactured by the method has the transparent window which is suitable for photochemical reaction, the manufacturing process is simple, the packaging cost is low, and the light transmittance, the sealing performance and the durability of the packaged micro-reactor are good; then the catalyst is loaded on the rough surface of the ceramic and the micro-channel is transparently packaged, the efficiency of photodegradation of organic matters in the water body is improved by using the catalyst wall-hanging ceramic micro-reactor, and the photodegradation reaction is carried out by using the method, so that the method has the characteristics of short reaction residence time, continuous reaction, no need of recovering the catalyst and long-term effectiveness.
2. The ceramic substrate containing the micro-channels is prepared by adopting alumina powder, cordierite powder, titanium dioxide and methylcellulose powder, and then by compression molding and mechanical micromachining, the materials used in the method are simple and easy to obtain, and the step of firing cordierite is omitted by adopting industrial cordierite powder. And then loading a photodegradation catalyst on the micro-channel on the ceramic substrate, protecting the appearance of the micro-channel by means of low-boiling paraffin, and curing and packaging the high-permeability resin to form the ceramic micro-reactor with the transparent window. Compared with the conventional alumina composite ceramic material, the ceramic microreactor manufactured by the method has the advantages that the sintering performance of the ceramic is improved by adding cordierite, and the problem of easy deformation in the sintering process of the composite ceramic material is solved. The sintering temperature and the heat preservation time are reduced on the basis of ensuring the performance of the composite ceramic material, so that the production process is further simplified. The ceramic microreactor manufactured by the method comprises a transparent window and is suitable for photochemical reaction, and the catalyst is coated by using a dropping mode, so that the catalyst is coated more uniformly. Compared with the conventional micro-channel packaging mode, the resin has better ultraviolet light transmittance, low overall packaging cost and good sealing property and durability; and the prepared micro-reactor can ensure that fluid passes through without liquid mixing, and is suitable for photocatalytic degradation reaction.
3. The reaction system of the ceramic microreactor containing the transparent window is a liquid phase reaction system, and liquid phase reactants are injected into the ceramic microreactor containing the transparent window through a microfluidic pump, and the photodegradation catalyst generates free radical oxidation degradation organic matters under illumination. The method for improving the efficiency of photodegradation of organic matters in water by using the catalyst wall-hanging ceramic-based microreactor by means of ceramic rough surface supported catalyst and transparent encapsulation of micro-channels has the advantages of short reaction residence time, continuous reaction, no need of catalyst recovery and long-term effectiveness, so as to overcome the defects of the prior art.
Drawings
FIG. 1 is a block diagram of a ceramic microreactor of the present invention;
FIG. 2 is a schematic view of the micro-channel structure of the ceramic microreactor of the present invention;
FIG. 3 is a flow chart of the photodegradation reaction performed by the ceramic microreactor of the present invention;
FIG. 4 is a graph showing the degradation process of the ceramic microreactor in the invention, wherein the non-illumination zone is an adsorption equilibrium stage and the illumination zone is a photodegradation stage;
in the figure: 1-ceramic substrate, 2-microchannel.
Detailed Description
The technical solution of the present invention is further described below, but the scope of the claimed invention is not limited to the above.
The fabrication of the ceramic microreactor as shown in FIGS. 1-2 includes the following specific examples:
example 1: the preparation process of ceramic micro reactor with transparent window includes the following steps:
preparing a ceramic substrate material:
according to the weight portions, 75 portions of alumina powder, 15 portions of cordierite powder, 2 portions of titanium dioxide and 1 portion of methyl cellulose powder are mixed, the alumina powder and the cordierite powder are all of industrial grade, the titanium dioxide is analytically pure, the viscosity of the methyl cellulose is 40000 MPa.s, the mixture is ball-milled for 4 hours and then passes through a 3000-mesh screen, water, ethanol and propanol are added for vacuum pugging, and the mixture is aged to obtain a ceramic substrate material;
step two, manufacturing the ceramic substrate 1 with the micro-channels 2:
placing a ceramic substrate material into a mould for compression molding to manufacture a ceramic green body, demolding the ceramic green body with the diameter of 60mm and the thickness of 3mm, drying the ceramic green body at 70 ℃, polishing the dried green body to be smooth by using 150-mesh and 2000-mesh sand paper, machining a micro-channel 2 by using a machining method, machining the micro-channel 2 by using a cutter with the diameter of 0.2-1 mm, wherein the wall thickness of the channel is larger than 4mm, reserving a volatile pore canal of a filling material, overflowing the pore canal with the diameter of 0.5-2.5mm, placing the micro-channel 2 into a high-temperature furnace for sintering, wherein the heating rate is 4 ℃/min, the temperature is 350 ℃ for 25min for glue discharging, the temperature is 3 ℃/min, the temperature is 950 ℃ for 25min for presintering, the temperature is 3 ℃/min, the temperature is 1300 ℃ for 0.5h for sintering, and naturally cooling to obtain the ceramic substrate 1 containing the micro-channel 2;
step three, the micro-channel 2 carries a catalyst, and the ceramic micro-reactor is packaged and molded:
mixing and stirring titanium dioxide catalyst, water, isopropanol and polyvinyl alcohol to prepare suspension, dripping the suspension into a micro-channel 2 loaded on a ceramic substrate 1, drying at 70 ℃, repeating for 2 times, filling molten liquid paraffin into the micro-channel 2 on the ceramic substrate 1, covering resin on the surface of the filled ceramic substrate 1, curing for 16 hours at 15 ℃, placing into a baking oven at 40 ℃ for heating and curing for 3 hours, heating to 50 ℃ for removing filling substances in the micro-channel 2 after curing, volatilizing the filling, cleaning, and drying to obtain the ceramic microreactor.
Example 2: the preparation process of ceramic micro reactor with transparent window includes the following steps:
(1) Preparing a ceramic substrate material:
mixing 80 parts of alumina powder, 20 parts of cordierite powder, 4 parts of titanium dioxide and 1.5 parts of methyl cellulose powder according to parts by weight, wherein the alumina powder and the cordierite powder are industrial grade, the titanium dioxide is analytically pure, the viscosity of the methyl cellulose is 40000 MPa.s, ball milling is carried out for 4 hours, sieving with a 3000-mesh sieve, adding water, ethanol and propanol, vacuum pugging, and aging to obtain a ceramic substrate material;
(2) Manufacturing a ceramic substrate 1 containing a microchannel 2:
placing a ceramic substrate material into a mould for compression molding to manufacture a ceramic green body, demolding the ceramic green body with the diameter of 60mm and the thickness of 5mm, drying the ceramic green body at the temperature of 85 ℃, polishing the dried green body to be smooth by using 150-mesh and 2000-mesh sand paper, machining a micro-channel 2 by using a machining method, machining the micro-channel 2 by using a cutter with the diameter of 0.2-1 mm, wherein the wall thickness of the channel is larger than 4mm, reserving a volatile pore canal of a filling material, overflowing the pore canal with the diameter of 0.5-2.5mm, placing the micro-channel 2 into a high-temperature furnace for sintering, wherein the heating rate is 5 ℃/min, the temperature of 400 ℃ is kept for 30min, the heating rate is 4 ℃/min, the temperature of 1000 ℃ is kept for 30min, the heating rate is 4 ℃/min, the heating rate is 1300-1450 ℃ is kept for 1h, and naturally cooling to obtain a ceramic substrate 1 containing the micro-channel 2;
(3) And (3) loading a catalyst on the microchannel 2, and packaging and forming a ceramic microreactor:
mixing and stirring a titanium-tin catalyst, water, isopropanol and polyvinyl alcohol to prepare a suspension, dripping the suspension into a micro-channel 2 loaded on a ceramic substrate 1, drying at 80 ℃ for 3 times, filling molten liquid paraffin into the micro-channel 2 on the ceramic substrate 1, covering resin on the surface of the filled ceramic substrate 1, curing for 24 hours at 20 ℃, placing into a 60 ℃ oven for heating and curing for 4 hours, heating to 70 ℃ after curing, removing filling substances in the micro-channel 2, volatilizing the filling substances, cleaning, and drying to obtain the ceramic microreactor.
Example 3: the manufacturing method of the ceramic microreactor comprises the following steps:
preparing a ceramic substrate material:
according to the weight portions, 85 portions of alumina powder, 25 portions of cordierite powder, 6 portions of titanium dioxide and 2 portions of methyl cellulose powder are mixed, the alumina powder and the cordierite powder are all of industrial grade, the titanium dioxide is analytically pure, the viscosity of the methyl cellulose is 40000 MPa.s, the mixture is ball-milled for 4 hours and then passes through a 3000-mesh screen, water, ethanol and propanol are added for vacuum pugging, and the mixture is aged to obtain a ceramic substrate material;
step two, manufacturing the ceramic substrate 1 with the micro-channels 2:
placing a ceramic substrate material into a mould for compression molding to manufacture a ceramic green body, demolding the ceramic green body with the diameter of 60mm and the thickness of 13mm, drying the ceramic green body at the temperature of 100 ℃, polishing the dried green body to be smooth by using 150-mesh and 2000-mesh sand paper, machining a micro-channel 2 by using a machining method, machining the micro-channel 2 by using a cutter with the diameter of 0.2mm-1mm, wherein the wall thickness of the channel is larger than 4mm, reserving a volatile pore canal of a filling material, overflowing the pore canal with the diameter of 0.5-2.5mm, placing the micro-channel 2 into a high-temperature furnace for sintering, wherein the heating rate is 6 ℃/min, the temperature is 450 ℃, the temperature is kept for 35min, the heating rate is 5 ℃/min, the temperature is kept for 35min, the temperature is kept for 1.5h, and then naturally cooling to obtain a ceramic substrate 1 containing the micro-channel 2;
step three, a micro-channel carries a catalyst, and packaging and forming of a ceramic micro-reactor:
mixing and stirring a titanium tin/GO catalyst, water, isopropanol and polyvinyl alcohol to prepare a suspension, dripping the suspension into a micro-channel 2 loaded on a ceramic substrate 1, drying at 90 ℃, repeating for 4 times, filling molten liquid paraffin into the micro-channel 2 on the ceramic substrate 1, covering resin on the surface of the filled ceramic substrate 1, curing at 25 ℃ for 36 hours, putting into a 90 ℃ oven for heating and curing for 6 hours, heating to 90 ℃ after curing, removing filling substances in the micro-channel 2, volatilizing the filling substances, cleaning, and drying to obtain the ceramic microreactor.
FIG. 3 is a flow chart of the photodegradation reaction performed by the ceramic microreactor of the present invention; FIG. 4 is a graph showing the degradation process of the ceramic microreactor in the invention, wherein the non-illumination zone is an adsorption equilibrium stage and the illumination zone is a photodegradation stage; according to the photodegradation reaction process shown in fig. 3 to 4, the ceramic microreactors prepared in the above examples are subjected to photodegradation reaction, respectively, and specific examples are as follows:
example 4: the ceramic microreactor (loaded with titanium dioxide catalyst) realizes photodegradation of organic dye wastewater, liquid-phase rhodamine B dye wastewater used for reaction is injected into the microreactor through a micro-flow peristaltic pump at a flow rate of 60 mu L/min, the reaction residence time is 1-20min, and the pressure of the reactor is normal pressure; vertically irradiating the micro-channel by using an ultraviolet lamp with the wavelength of 365nm and the power of 10w, wherein the distance between a light source and the channel is 1mm, and carrying out degradation reaction under illumination;
the reacted sample is detected by an ultraviolet spectrophotometer, and the degradation degree is judged by the concentration corresponding to absorbance. The efficiency of photodegradation rhodamine B under the above conditions of the microreactor loaded with the titanium dioxide catalyst is 23%.
Example 5: the ceramic microreactor (loaded with titanium-tin catalyst) realizes photodegradation of organic dye wastewater, liquid-phase rhodamine B dye wastewater used in the reaction is injected into the microreactor through a micro-flow peristaltic pump at a flow rate of 40 mu L/min, the reaction residence time is 1-20min, and the pressure of the reactor is normal pressure; vertically irradiating the micro-channel by using an ultraviolet lamp with the wavelength of 365nm and the power of 10w, wherein the distance between a light source and the channel is 1mm, and carrying out degradation reaction under illumination;
the efficiency of photodegradation rhodamine B in the micro-reactor loaded with the titanium-tin catalyst under the above conditions is 27.3 percent.
Example 6: the ceramic microreactor (titanium tin/GO catalyst is loaded: titanium tin catalyst taking graphene oxide as a template) realizes photodegradation of organic dye wastewater, liquid-phase rhodamine B dye wastewater used in the reaction is injected into the microreactor through a micro-flow peristaltic pump at a flow rate of 40 mu L/min, the reaction residence time is 1-20min, and the pressure of the reactor is normal pressure; vertically irradiating the micro-channel by using an ultraviolet lamp with the wavelength of 365nm and the power of 10w, wherein the distance between a light source and the channel is 1mm, and carrying out degradation reaction under illumination;
the micro-reactor loaded with the titanium-tin catalyst taking graphene oxide as a template has the photodegradation rhodamine B efficiency of 46% under the above conditions, and the degradation process curve of the micro-reactor of the embodiment 3 is shown in fig. 4, wherein the non-illumination interval is an adsorption equilibrium stage; the illumination interval is the photodegradation stage.
Claims (10)
1. The manufacturing method of the ceramic microreactor is characterized by comprising the following steps:
preparing a ceramic substrate material:
mixing 75-85 parts of alumina powder, 15-25 parts of cordierite powder, 2-6 parts of titanium dioxide and 1-2 parts of methylcellulose powder according to parts by weight, ball milling, sieving, adding water, ethanol and propanol, performing vacuum pugging, and aging to obtain a ceramic substrate material;
step two, manufacturing a ceramic substrate containing micro channels:
putting the ceramic substrate material obtained in the previous step into a mould for compression molding to manufacture a ceramic green body, drying the ceramic green body at 70-100 ℃ after demoulding, polishing the ceramic green body to be smooth by using sand paper after the ceramic green body is dried, machining the micro-channel on the ceramic green body, and then placing the machined ceramic green body into a high-temperature furnace for sintering, wherein the sintering process is as follows: firstly, heating to 350-450 ℃ at a heating rate of 4-6 ℃/min, and then preserving heat for 25-35min to perform glue discharging on the ceramic green embryo; then heating to 950-1050 ℃ at a heating rate of 3-5 ℃/min, and preserving heat for 25-35min to perform pre-sintering of the ceramic green body; then heating to 1300-1450 ℃ at a heating rate of 3-5 ℃/min, preserving heat for 0.5-1.5h, sintering the ceramic green body, and naturally cooling after the sintering is completed to obtain the ceramic substrate containing the micro-channels;
step three, a micro-channel carries a catalyst, and packaging and forming of a ceramic micro-reactor:
preparing a photodegradation catalyst into a suspension, dripping the suspension into a micro-channel loaded on the ceramic substrate obtained in the previous step, drying at 70-90 ℃, and repeating for 2-4 times; filling molten liquid paraffin into a micro-channel dropwise added on a ceramic substrate of suspension, covering resin on the surface of the ceramic substrate filled with paraffin, curing at 15-25 ℃ for 16-36h, placing the ceramic substrate covered with resin into a baking oven at 40-90 ℃ for heating and curing for 3-6h, heating to 50-90 ℃ after curing is finished, removing the filler in the micro-channel, and cleaning and drying after the filler volatilizes to obtain the ceramic microreactor.
2. The method for manufacturing a ceramic microreactor according to claim 1, wherein: in the first step, the alumina powder and the cordierite powder are industrial grade, the titanium dioxide is of analytical grade, and the viscosity of the methylcellulose is 40000 MPa.s; in the mixing, 80 parts of alumina powder, 20 parts of cordierite powder, 4 parts of titanium dioxide and 1.5 parts of methylcellulose powder are mixed according to parts by weight; ball milling was performed for 4 hours, followed by sieving with a 3000 mesh screen.
3. The method for manufacturing a ceramic microreactor according to claim 1, wherein: in the second step, the prepared ceramic green body is round, the diameter of the ceramic green body is 60mm, and the thickness of the ceramic green body is 3-13mm; and (3) polishing the dried ceramic green blank by using 150-mesh sand paper, and then polishing the ceramic green blank by using 2000-mesh sand paper.
4. The method for manufacturing a ceramic microreactor according to claim 1, wherein: in the second step, when the micro-channel is machined by using a machining method, a cutter with the diameter of phi of 0.2-1 mm is used, the wall thickness of the machined micro-channel is more than 4mm, a volatile pore canal of the filling material needs to be reserved, and the diameter of an overflow pore canal is 0.5-2.5mm.
5. The method for manufacturing a ceramic microreactor according to claim 1, wherein: in the second step, the ceramic green body after being processed is placed in a high-temperature furnace for sintering, and the process comprises the following steps: firstly, heating to 400 ℃ at a heating rate of 5 ℃/min, and then preserving heat for 30min to perform glue discharging on the ceramic green body; then heating to 1000 ℃ at a heating rate of 4 ℃/min, and then preserving heat for 30min to perform pre-sintering of the ceramic green body; then heating to 1300-1450 ℃ at a heating rate of 4 ℃/min, preserving heat for 1h, sintering the ceramic green body, and naturally cooling to obtain the ceramic substrate containing the micro-channels.
6. The method for manufacturing a ceramic microreactor according to claim 1, wherein: the micro-channel processed in the second step is a serpentine channel with the width of 0.5mm, the height of 0.8mm and the length of 20-60 mm.
7. The method for manufacturing a ceramic microreactor according to claim 1, wherein: in the third step, the photodegradation catalyst, water, isopropanol and polyvinyl alcohol are mixed and stirred to prepare a suspension, the suspension is dripped into a micro-channel loaded on a ceramic substrate, and the suspension is dried at 80 ℃ and repeated for 3 times.
8. The method for manufacturing a ceramic microreactor according to claim 1, wherein: in the third step, resin is covered on the surface of the ceramic substrate after filling, then the ceramic substrate is cured for 24 hours at 20 ℃, then the ceramic substrate is put into a 60 ℃ oven for heating and curing for 4 hours, and the ceramic substrate is heated to 70 ℃ after curing to remove filling substances in the micro-channels.
9. Use of a ceramic microreactor prepared by a method for manufacturing a ceramic microreactor according to any one of claims 1 to 8, characterized in that: and injecting a liquid-phase reactant into the ceramic microreactor through a microfluidic pump by using a liquid-phase reaction system, and photodegradation the catalyst under illumination to generate free radical oxidation degradation organic matters.
10. The use of a ceramic microreactor according to claim 9, characterized in that: the micro-flow pump is a micro-flow peristaltic pump, and the flow rate of the liquid phase is 20-200 mu L/min; the reaction residence time of the liquid phase reactant in the ceramic micro-reactor is 1-20min, and the pressure of the ceramic micro-reactor is controlled below 3bar when the reaction is carried out.
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| JP2004202813A (en) * | 2002-12-25 | 2004-07-22 | Hitachi Metals Ltd | Method for manufacturing ceramic sintered compact with comb tooth-like passage |
| DE102007049172A1 (en) * | 2007-10-13 | 2009-04-16 | Micro Systems Engineering Gmbh & Co. Kg | A microreactor and method of making the same and method of making a substrate for a microreactor |
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| FR2913109B1 (en) * | 2007-02-27 | 2009-05-01 | Boostec Sa | METHOD FOR MANUFACTURING A CERAMIC HEAT EXCHANGER DEVICE AND DEVICES OBTAINED BY THE METHOD |
| CN101768275A (en) * | 2010-01-25 | 2010-07-07 | 中国人民解放军国防科学技术大学 | Precursor polymer for manufacturing fine ceramic components and synthesis method thereof |
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| JP2004202813A (en) * | 2002-12-25 | 2004-07-22 | Hitachi Metals Ltd | Method for manufacturing ceramic sintered compact with comb tooth-like passage |
| DE102007049172A1 (en) * | 2007-10-13 | 2009-04-16 | Micro Systems Engineering Gmbh & Co. Kg | A microreactor and method of making the same and method of making a substrate for a microreactor |
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