CN113828260A - Manufacturing method and application of ceramic microreactor - Google Patents
Manufacturing method and application of ceramic microreactor Download PDFInfo
- Publication number
- CN113828260A CN113828260A CN202111289912.1A CN202111289912A CN113828260A CN 113828260 A CN113828260 A CN 113828260A CN 202111289912 A CN202111289912 A CN 202111289912A CN 113828260 A CN113828260 A CN 113828260A
- Authority
- CN
- China
- Prior art keywords
- ceramic
- microreactor
- micro
- green body
- channel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Catalysts (AREA)
Abstract
A manufacturing method of a ceramic micro-reactor and application thereof are provided, wherein the manufacturing method comprises the steps of preparing a ceramic substrate material, manufacturing a ceramic substrate containing a micro-channel, and packaging and molding a micro-channel loaded catalyst and the ceramic micro-reactor. 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 transmission, sealing property and durability; then, by means of loading a catalyst on the rough surface of the ceramic and carrying out transparent packaging of the microchannel, the method for improving the efficiency of degrading organic matters in the water body by using the wall-mounted ceramic microreactor of the catalyst is utilized to carry out the photodegradation reaction, and the method has the beneficial effects of short reaction residence time, continuous reaction, no need of recovering the catalyst and long-term effectiveness.
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 severe. Remediation of industrial, agricultural and life-borne water pollution has attracted attention from all parties. Wherein the organic wastewater generated in industrial production has high toxicity, high chromaticity, large pH value change and serious environmental pollution. Photocatalytic oxidation treatment of organic wastewater with a photocatalyst is considered to be a relatively inexpensive and effective method. The photocatalytic water treatment technology is an environment-friendly chemical treatment method, a small amount of catalyst can be used in a short time, and the pollution of organic matters to water is efficiently treated; however, when the conventional reactor is used for carrying out photodegradation treatment, the problems of difficult catalyst recovery, secondary pollution to equipment, low intermittent reaction efficiency and the like exist, the problems of low light energy utilization rate, photon transfer limitation, lack of a reaction path due to oxygen deficiency and the like also exist, the advantages of high-efficiency mass transfer efficiency, short diffusion time, a controllable reaction path and the like of the microreactor provide a feasible solution for the microreactor, 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 microreactor to be applied to a harsh reaction environment, so that the application of the microreactor to the photodegradation reaction is considered. At first glance, the micro-reaction technology and water treatment seem to be contradictory, as the former is designed for handling small amounts of solution, while the latter requires mass production. This mismatch can be compensated by enlarging the microreactor.
Although the photocatalytic water treatment technology is an environment-friendly chemical treatment method, the problems of low light energy utilization rate, photon transfer limitation, lack of a reaction path due to oxygen deficiency and the like exist, a feasible solution is provided for the micro-reactor by the advantages of high-efficiency mass transfer efficiency, short diffusion time, a controllable reaction path and the like, the rough surface and certain porosity of the ceramic material are convenient for loading of a 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 micro-reactor is considered to be applied to a photodegradation reaction. At present, micro machining of ceramic materials is complex, after the ceramic materials are machined into micro channels, the micro channels are difficult to seal and easy to collapse in the sintering process, and the equipment and the process are complex and high in cost due to the use of isostatic pressing integrated sintering; the high-strength gasket is used for pressing and sealing, so that the weather resistance is poor; the performance of the ceramic micro-reactor is directly influenced by the packaging mode of the ceramic micro-channel due to the use of adhesive, high temperature resistance and poor 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:
step one, 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 the ceramic substrate with the micro-channels:
putting the ceramic substrate material obtained in the last step into a mould for mould pressing and forming to manufacture a ceramic green body, drying the ceramic green body at 70-100 ℃ after demoulding, polishing the ceramic green body to be flat by using sand paper after drying the ceramic green body, machining a micro-channel on the ceramic green body by using machining, then placing the machined ceramic green body in a high-temperature furnace for sintering, wherein the sintering process is as follows: heating to 350-; then raising the temperature to 950-1050 ℃ at the heating rate of 3-5 ℃/min, and then preserving the heat for 25-35min to perform pre-sintering on the ceramic green body; then heating to 1300-1450 ℃ at the heating rate of 3-5 ℃/min, preserving the heat for 0.5-1.5h, sintering the ceramic green body, and naturally cooling after sintering to obtain the ceramic substrate containing the micro-channel;
thirdly, loading a catalyst on the microchannel, and packaging and molding the ceramic microreactor:
preparing a light degradation catalyst into a suspension, dropwise adding the suspension into the microchannel 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 the micro-channel on the ceramic substrate into which the suspension is dripped, then covering resin on the surface of the ceramic substrate filled with the paraffin, curing at 15-25 ℃ for 16-36h, putting the ceramic substrate covered with the resin into a drying oven at 40-90 ℃ for heating and curing for 3-6h, heating to 50-90 ℃ after curing is completed to remove the filler in the micro-channel, and cleaning and drying after the filler is volatilized to obtain the ceramic microreactor.
Further, in the first step, the used alumina powder and cordierite powder are both in industrial grade, titanium dioxide is in analytical purity grade, and the viscosity of methyl cellulose is 40000MPa & s; when mixing, mixing 80 parts of alumina powder, 20 parts of cordierite powder, 4 parts of titanium dioxide and 1.5 parts of methyl cellulose powder in parts by weight; the ball milling was carried out for 4h, followed by sieving using a 3000 mesh sieve.
Further, in the second step, the prepared ceramic green body is circular, the diameter of the ceramic green body is 60mm, and the thickness of the ceramic green body is 3-13 mm; the dried ceramic green body is firstly polished by 150-mesh abrasive paper and then polished to be smooth by 2000-mesh abrasive paper.
Furthermore, in the second step, when the micro-channel is machined by a mechanical machining method, a cutter with the diameter of phi 0.2mm-1mm is used, the wall thickness of the machined micro-channel is larger than 4mm, a volatilization pore channel of the filling material needs to be reserved, and the diameter of the overflow pore channel is 0.5-2.5 mm.
Further, in the second step, the process of placing the processed ceramic green body in a high temperature furnace for sintering is as follows: heating to 400 ℃ at a heating rate of 5 ℃/min, and then preserving heat for 30min to carry out rubber discharge on the ceramic green body; then raising the temperature to 1000 ℃ at the heating rate of 4 ℃/min, and then preserving the heat for 30min to perform pre-sintering on the ceramic green body; then heating to 1300-1450 ℃ at the heating rate of 4 ℃/min, preserving the heat for 1h to sinter the ceramic green body, and then naturally cooling to obtain the ceramic substrate containing the micro-channel.
Furthermore, 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.
Further, 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 the microchannel loaded on the ceramic substrate, and the drying is carried out at 80 ℃ and repeated for 3 times.
Further, in the third step, the resin is covered on the surface of the filled ceramic substrate, then the ceramic substrate is cured for 24 hours at the temperature of 20 ℃, then the ceramic substrate is placed into a 60 ℃ oven for heating and curing for 4 hours, and after curing, the ceramic substrate is heated to 70 ℃ to remove the filling materials in the micro-channels.
According to the application of the ceramic microreactor prepared by the manufacturing method of any one of the ceramic microreactors, a liquid-phase reaction system is used, a liquid-phase reactant is injected into the ceramic microreactor through a micro-flow pump, and a photodegradation catalyst generates free radicals to oxidize and degrade organic matters under illumination.
Further, the micro-flow pump is a micro-flow peristaltic pump, and the flow rate of a liquid phase is 20-200 mu L/min; the reaction residence time of the liquid phase reactant in the ceramic microreactor is 1-20min, and the pressure of the ceramic microreactor is controlled below 3bar when the reaction is carried out.
The invention has the beneficial effects that: 1. the invention protects the appearance of the microchannel by means of low-boiling-point paraffin, and the high-transparency resin is cured and packaged to form the ceramic microreactor with the transparent window, the ceramic microreactor manufactured by the method contains the transparent window and is suitable for photochemical reaction, the manufacturing process is simple, the packaging cost is low, and the packaged microreactor has good light transmittance, sealing property and durability; then, by means of loading a catalyst on the rough surface of the ceramic and carrying out transparent packaging of the microchannel, the method for improving the efficiency of degrading organic matters in the water body by using the wall-mounted ceramic microreactor of the catalyst is utilized to carry out the photodegradation reaction, and 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 material is prepared by adopting alumina powder, cordierite powder, titanium dioxide and methyl cellulose powder, and then the ceramic substrate containing the micro-channel is prepared by compression molding and mechanical micromachining. And then loading a photodegradation catalyst on a microchannel on the ceramic substrate, protecting the appearance of the microchannel by means of low-boiling-point paraffin, and curing and packaging the high-transparency resin to form the ceramic microreactor with a 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 of the composite ceramic material in the sintering process 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 contains a transparent window suitable for photochemical reaction, and the method coats the catalyst in a dropwise manner, so that the catalyst is coated more uniformly. Compared with the conventional micro-channel packaging mode, the resin selected by the invention has better ultraviolet light transmission, low overall packaging cost, good sealing property and durability; and proved by experiments, the manufactured micro-reactor can ensure that fluid can not cross fluid when passing through the micro-reactor, and is suitable for photocatalytic degradation reaction.
3. The reaction system of the ceramic microreactor with the transparent window is a liquid phase reaction system, a liquid phase reactant is injected into the ceramic microreactor with the transparent window through a micro-flow pump, and a photodegradation catalyst generates free radicals to oxidize and degrade organic matters under illumination. The method for improving the efficiency of degrading organic matters in water by light by means of loading a catalyst on the rough surface of ceramic and carrying out transparent packaging of a microchannel, and the wall-mounted ceramic-based microreactor of the catalyst is used for carrying out light degradation reaction, so that the reaction residence time is short, the reaction is continuous, the catalyst does not need to be recycled, and the method is effective for a long time, and the defects of the prior art are overcome.
Drawings
FIG. 1 is a schematic diagram of a ceramic microreactor of the present invention;
FIG. 2 is a schematic diagram of a ceramic microreactor microchannel structure of the present invention;
FIG. 3 is a flow chart of a photodegradation reaction of a ceramic microreactor of the present invention;
FIG. 4 is a graph showing the process of degradation of a ceramic microreactor according to the present invention, wherein the non-illuminated region is an adsorption equilibrium stage and the illuminated region 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 described.
The fabrication of the ceramic microreactor shown in fig. 1-2 includes the following specific examples:
example 1: a method for manufacturing a ceramic microreactor with a transparent window comprises the following steps:
step one, preparing a ceramic substrate material:
mixing 75 parts of alumina powder, 15 parts of cordierite powder, 2 parts of titanium dioxide and 1 part of methylcellulose powder, wherein the alumina powder and the cordierite powder are both in industrial grade, the titanium dioxide is analytically pure, the viscosity of the methylcellulose is 40000MPa & s, the mixture is ball-milled for 4 hours, then the mixture is filtered by a 3000-mesh screen, and water, ethanol and propanol are added into the mixture for vacuum pugging and aging to obtain a ceramic substrate material;
step two, manufacturing the ceramic substrate 1 containing the micro-channel 2:
putting a ceramic substrate material into a mould for compression moulding to manufacture a ceramic green body, wherein the diameter of the ceramic green body is 60mm and the thickness of the ceramic green body is 3mm, drying the ceramic green body at 70 ℃ after demoulding, polishing and flattening the dried green body by using 150-mesh and 2000-mesh abrasive paper, then 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 more than 4mm, a volatile pore channel of a filling material is reserved, the diameter of an overflow pore channel is 0.5-2.5mm, the micro-channel 2 is a snake-shaped channel with the width of 0.5mm, the height of 0.8mm and the length of 20-60mm, sintering the processed ceramic green body in a high-temperature furnace, heating to 350 ℃, keeping the temperature for 25min at 3 ℃/min, heating to 950 ℃ for keeping the temperature for presintering, the heating rate is 3 ℃/min, the temperature is increased to 1300 ℃, the temperature is preserved for 0.5h for sintering, and then the ceramic substrate 1 containing the micro-channel 2 is obtained after natural cooling;
step three, loading a catalyst on the microchannel 2, packaging and molding the ceramic microreactor:
mixing and stirring a titanium dioxide catalyst, water, isopropanol and polyvinyl alcohol to prepare a suspension, dropwise adding the suspension into a microchannel 2 loaded on a ceramic substrate 1, drying at 70 ℃, repeating for 2 times, filling molten liquid paraffin into the microchannel 2 on the ceramic substrate 1, covering resin on the surface of the filled ceramic substrate 1, curing at 15 ℃ for 16 hours, putting the ceramic substrate 1 into a 40 ℃ oven for heating and curing for 3 hours, heating to 50 ℃ after curing to remove filling materials in the microchannel 2, volatilizing the filling materials, cleaning and drying to obtain the ceramic microreactor.
Example 2: a method for manufacturing a ceramic microreactor with a transparent window comprises 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 methylcellulose powder, wherein the alumina powder and the cordierite powder are both in industrial grade, the titanium dioxide is analytically pure, the viscosity of the methylcellulose is 40000MPa & s, the mixture is ball-milled for 4 hours, then the mixture is sieved by a 3000-mesh sieve, and water, ethanol and propanol are added for vacuum pugging and aging to obtain a ceramic substrate material;
(2) production of ceramic substrate 1 containing microchannel 2:
putting a ceramic substrate material into a mould for compression moulding to manufacture a ceramic green body, wherein the diameter of the ceramic green body is 60mm and the thickness of the ceramic green body is 5mm, the ceramic green body is dried at 85 ℃ after demoulding, the dried green body is polished and leveled by 150-mesh and 2000-mesh abrasive paper, then a micro-channel 2 is machined by using a machining method, the micro-channel 2 is machined by using a machining method, a cutter with the diameter of 0.2mm-1mm is used for machining the micro-channel 2, the wall thickness of the channel is more than 4mm, a volatilization pore channel of a filling material is reserved, the diameter of an overflow pore channel is 0.5-2.5mm, the micro-channel 2 is a snake-shaped channel with the width of 0.5mm, the height of 0.8mm and the length of 20-60mm, the processed ceramic green body is placed in a high-temperature furnace for sintering, the heating rate is 5 ℃/min, the temperature is increased to 400 ℃, the temperature is maintained for 30min, the temperature is increased to 1000 ℃, the temperature is maintained for 30min, the heating rate is 4 ℃/min, the temperature is increased to 1300-;
(3) the microchannel 2 is loaded with a catalyst, and the ceramic microreactor is packaged and molded:
mixing and stirring a titanium tin catalyst, water, isopropanol and polyvinyl alcohol to prepare a suspension, dropwise adding the suspension into a microchannel 2 loaded on a ceramic substrate 1, drying at 80 ℃, repeating for 3 times, filling molten liquid paraffin into the microchannel 2 on the ceramic substrate 1, covering resin on the surface of the filled ceramic substrate 1, curing at 20 ℃ for 24 hours, putting the ceramic substrate 1 into a 60 ℃ oven for heating and curing for 4 hours, heating to 70 ℃ after curing to remove filling materials in the microchannel 2, volatilizing the filling materials, cleaning and drying to obtain the ceramic microreactor.
Example 3: a manufacturing method of a ceramic microreactor comprises the following steps:
step one, preparing a ceramic substrate material:
mixing 85 parts of alumina powder, 25 parts of cordierite powder, 6 parts of titanium dioxide and 2 parts of methylcellulose powder, wherein the alumina powder and the cordierite powder are both in industrial grade, the titanium dioxide is analytically pure, the viscosity of the methylcellulose is 40000MPa & s, the mixture is ball-milled for 4 hours, then the mixture is filtered by a 3000-mesh screen, and water, ethanol and propanol are added for vacuum pugging and aging to obtain a ceramic substrate material;
step two, manufacturing the ceramic substrate 1 containing the micro-channel 2:
putting a ceramic substrate material into a mould for compression moulding to manufacture a ceramic green body, wherein the diameter of the ceramic green body is 60mm and the thickness of the ceramic green body is 13mm, drying the ceramic green body at 100 ℃ after demoulding, polishing and flattening the dried green body by using 150-mesh and 2000-mesh abrasive paper, then 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 more than 4mm, a volatile pore channel of a filling material is reserved, the diameter of an overflow pore channel is 0.5-2.5mm, the micro-channel 2 is a snake-shaped channel with the width of 0.5mm, the height of 0.8mm and the length of 20-60mm, sintering the processed ceramic green body in a high-temperature furnace, heating up to 450 ℃, keeping the temperature for 35min at 5 ℃/min, heating up to 1050 ℃ and keeping the temperature for 35min for presintering, the heating rate is 5 ℃/min, the ceramic substrate is heated to 1450 ℃, the temperature is preserved for 1.5h for sintering, and then the ceramic substrate is naturally cooled to obtain a ceramic substrate 1 containing the micro-channel 2;
thirdly, loading a catalyst on the microchannel, and packaging and molding the ceramic microreactor:
mixing and stirring a titanium tin/GO catalyst, water, isopropanol and polyvinyl alcohol to prepare a suspension, dropwise adding the suspension into a microchannel 2 loaded on a ceramic substrate 1, drying at 90 ℃, repeating for 4 times, filling molten liquid paraffin into the microchannel 2 on the ceramic substrate 1, covering resin on the surface of the filled ceramic substrate 1, curing at 25 ℃ for 36 hours, putting the ceramic substrate into a 90 ℃ oven for heating and curing for 6 hours, heating to 90 ℃ after curing to remove filling materials in the microchannel 2, volatilizing the filling materials, cleaning and drying to obtain the ceramic microreactor.
FIG. 3 is a flow chart of a photodegradation reaction of a ceramic microreactor of the present invention; FIG. 4 is a graph showing the process of degradation of a ceramic microreactor according to the present invention, wherein the non-illuminated region is an adsorption equilibrium stage and the illuminated region is a photodegradation stage; according to the photodegradation reaction process shown in fig. 3-4, the ceramic microreactors prepared in the above examples are respectively subjected to photodegradation reaction, and specific examples are as follows:
example 4: the method comprises the following steps that (1) photodegradation of organic dye wastewater is realized by a ceramic microreactor (loaded with a titanium dioxide catalyst), liquid-phase rhodamine B dye wastewater used for reaction is injected into the microreactor through a micro-flow peristaltic pump at the 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 microchannel by using an ultraviolet lamp with the wavelength of 365nm and the power of 10w, wherein the height of a light source from the channel is 1mm, and performing degradation reaction under illumination;
and detecting the reacted sample by an ultraviolet spectrophotometer, and judging the degradation degree by the concentration corresponding to the absorbance. The efficiency of the microreactor loaded with the titanium dioxide catalyst for photodegradation of rhodamine B under the conditions is 23%.
Example 5: the method comprises the following steps that (1) photodegradation of organic dye wastewater is realized by a ceramic microreactor (loaded with a titanium-tin catalyst), liquid-phase rhodamine B dye wastewater used for reaction is injected into the microreactor through a micro-flow peristaltic pump at the 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 microchannel by using an ultraviolet lamp with the wavelength of 365nm and the power of 10w, wherein the height of a light source from the channel is 1mm, and performing degradation reaction under illumination;
the efficiency of the microreactor loaded with the titanium-tin catalyst for photodegradation of rhodamine B under the conditions is 27.3%.
Example 6: performing photodegradation on organic dye wastewater by using a ceramic microreactor (loaded with a titanium tin/GO catalyst: a titanium tin catalyst taking graphene oxide as a template), injecting liquid-phase rhodamine B dye wastewater used for reaction into the microreactor through a micro-flow peristaltic pump at the flow rate of 40 mu L/min, wherein the reaction residence time is 1-20min, and the pressure of the reactor is normal pressure; vertically irradiating the microchannel by using an ultraviolet lamp with the wavelength of 365nm and the power of 10w, wherein the height of a light source from the channel is 1mm, and performing degradation reaction under illumination;
the efficiency of the microreactor loaded with the titanium tin catalyst taking the graphene oxide as the template for photodegradation of rhodamine B under the above conditions is 46%, and the degradation process curve of the microreactor in the embodiment 3 is shown in fig. 4, wherein the non-illumination interval is an adsorption equilibrium stage; the light interval is the photodegradation phase.
Claims (10)
1. A manufacturing method of a ceramic microreactor is characterized by comprising the following steps:
step one, 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 the ceramic substrate with the micro-channels:
putting the ceramic substrate material obtained in the last step into a mould for mould pressing and forming to manufacture a ceramic green body, drying the ceramic green body at 70-100 ℃ after demoulding, polishing the ceramic green body to be flat by using sand paper after drying the ceramic green body, machining a micro-channel on the ceramic green body by using machining, then placing the machined ceramic green body in a high-temperature furnace for sintering, wherein the sintering process is as follows: heating to 350-; then raising the temperature to 950-1050 ℃ at the heating rate of 3-5 ℃/min, and then preserving the heat for 25-35min to perform pre-sintering on the ceramic green body; then heating to 1300-1450 ℃ at the heating rate of 3-5 ℃/min, preserving the heat for 0.5-1.5h, sintering the ceramic green body, and naturally cooling after sintering to obtain the ceramic substrate containing the micro-channel;
thirdly, loading a catalyst on the microchannel, and packaging and molding the ceramic microreactor:
preparing a light degradation catalyst into a suspension, dropwise adding the suspension into the microchannel 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 the micro-channel on the ceramic substrate into which the suspension is dripped, then covering resin on the surface of the ceramic substrate filled with the paraffin, curing at 15-25 ℃ for 16-36h, putting the ceramic substrate covered with the resin into a drying oven at 40-90 ℃ for heating and curing for 3-6h, heating to 50-90 ℃ after curing is completed to remove the filler in the micro-channel, and cleaning and drying after the filler is volatilized to obtain the ceramic microreactor.
2. The method of making a ceramic microreactor of claim 1, wherein: in the first step, the used alumina powder and cordierite powder are both in industrial grade, titanium dioxide is in analytical purity grade, and the viscosity of methyl cellulose is 40000MPa & s; when mixing, mixing 80 parts of alumina powder, 20 parts of cordierite powder, 4 parts of titanium dioxide and 1.5 parts of methyl cellulose powder in parts by weight; the ball milling was carried out for 4h, followed by sieving using a 3000 mesh sieve.
3. The method of making a ceramic microreactor of claim 1, wherein: in the second step, the prepared ceramic green body is circular, the diameter of the ceramic green body is 60mm, and the thickness of the ceramic green body is 3-13 mm; the dried ceramic green body is firstly polished by 150-mesh abrasive paper and then polished to be smooth by 2000-mesh abrasive paper.
4. The method of making a ceramic microreactor of claim 1, wherein: in the second step, when the micro-channel is machined by a mechanical machining method, a cutter with the diameter of phi 0.2mm-1mm is used, the wall thickness of the machined micro-channel is more than 4mm, a volatilization pore channel of the filling material needs to be reserved, and the diameter of the overflow pore channel is 0.5-2.5 mm.
5. The method of making a ceramic microreactor of claim 1, wherein: in the second step, the process of placing the processed ceramic green body in a high-temperature furnace for sintering is as follows: heating to 400 ℃ at a heating rate of 5 ℃/min, and then preserving heat for 30min to carry out rubber discharge on the ceramic green body; then raising the temperature to 1000 ℃ at the heating rate of 4 ℃/min, and then preserving the heat for 30min to perform pre-sintering on the ceramic green body; then heating to 1300-1450 ℃ at the heating rate of 4 ℃/min, preserving the heat for 1h to sinter the ceramic green body, and then naturally cooling to obtain the ceramic substrate containing the micro-channel.
6. The method of making a ceramic microreactor of 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 of making a ceramic microreactor of 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 the microchannel loaded on the ceramic substrate, and the drying is carried out at 80 ℃ and repeated for 3 times.
8. The method of making a ceramic microreactor of claim 1, wherein: and in the third step, covering the resin on the surface of the filled ceramic substrate, curing the resin at 20 ℃ for 24 hours, putting the ceramic substrate into a 60 ℃ oven, heating the ceramic substrate for curing for 4 hours, and heating the ceramic substrate to 70 ℃ after curing to remove the filling materials in the micro-channels.
9. Use of a ceramic microreactor manufactured by a method for manufacturing a ceramic microreactor according to any one of claims 1 to 8, wherein: and (3) injecting a liquid-phase reactant into the ceramic microreactor through a microflow pump by using a liquid-phase reaction system, and carrying out photodegradation on the catalyst to generate free radicals to oxidize and degrade organic matters under illumination.
10. Use of a ceramic microreactor according to claim 9, characterized in that: the micro-flow pump is a micro-flow peristaltic pump, and the liquid phase flow rate is 20-200 mu L/min; the reaction residence time of the liquid phase reactant in the ceramic microreactor is 1-20min, and the pressure of the ceramic microreactor is controlled below 3bar when the reaction is carried out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111289912.1A CN113828260B (en) | 2021-11-02 | 2021-11-02 | Manufacturing method and application of ceramic microreactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111289912.1A CN113828260B (en) | 2021-11-02 | 2021-11-02 | Manufacturing method and application of ceramic microreactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113828260A true CN113828260A (en) | 2021-12-24 |
| CN113828260B CN113828260B (en) | 2023-05-30 |
Family
ID=78966857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111289912.1A Active CN113828260B (en) | 2021-11-02 | 2021-11-02 | Manufacturing method and application of ceramic microreactor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113828260B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115106034A (en) * | 2022-06-23 | 2022-09-27 | 之江实验室 | Visual microreactor and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6736983B1 (en) * | 1999-05-28 | 2004-05-18 | Atotech Deutschland Gmbh | Method for producing microcomponents |
| 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 |
| 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 |
| US20100322829A1 (en) * | 2007-02-27 | 2010-12-23 | Boostec S.A. | Process for manufacturing a device of heat exchanger type made of ceramic, and devices obtained by the process |
| US20140045954A1 (en) * | 2012-08-07 | 2014-02-13 | Velocys, Inc. | Fischer-tropsch process |
| CN104353355A (en) * | 2014-11-14 | 2015-02-18 | 上海应用技术学院 | Ceramic purifier for purifying ozone in air and preparation method of ceramic purifier |
| CN110304935A (en) * | 2019-08-08 | 2019-10-08 | 贵州大学 | A kind of packaging method of ceramics microchannel |
| CN111266068A (en) * | 2020-03-04 | 2020-06-12 | 大连理工大学 | Micro-reactor of nano-structure micro-channel substrate grafted with supported catalyst and preparation method thereof |
| CN113336555A (en) * | 2021-06-24 | 2021-09-03 | 浙江大学 | Photocuring type 3D printing manufacturing method of integral SiC-based microreactor |
-
2021
- 2021-11-02 CN CN202111289912.1A patent/CN113828260B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6736983B1 (en) * | 1999-05-28 | 2004-05-18 | Atotech Deutschland Gmbh | Method for producing microcomponents |
| JP2004202813A (en) * | 2002-12-25 | 2004-07-22 | Hitachi Metals Ltd | Method for manufacturing ceramic sintered compact with comb tooth-like passage |
| US20100322829A1 (en) * | 2007-02-27 | 2010-12-23 | Boostec S.A. | Process for manufacturing a device of heat exchanger type made of ceramic, and devices obtained by the process |
| 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 |
| 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 |
| US20140045954A1 (en) * | 2012-08-07 | 2014-02-13 | Velocys, Inc. | Fischer-tropsch process |
| CN104353355A (en) * | 2014-11-14 | 2015-02-18 | 上海应用技术学院 | Ceramic purifier for purifying ozone in air and preparation method of ceramic purifier |
| CN110304935A (en) * | 2019-08-08 | 2019-10-08 | 贵州大学 | A kind of packaging method of ceramics microchannel |
| CN111266068A (en) * | 2020-03-04 | 2020-06-12 | 大连理工大学 | Micro-reactor of nano-structure micro-channel substrate grafted with supported catalyst and preparation method thereof |
| CN113336555A (en) * | 2021-06-24 | 2021-09-03 | 浙江大学 | Photocuring type 3D printing manufacturing method of integral SiC-based microreactor |
Non-Patent Citations (1)
| Title |
|---|
| JUN WANG ET AL.: "Fabrication of ceramic microcomponents and microreactor for the steam reforming of ethanol", 《MICROSYSTEM TECHNOLOGIES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115106034A (en) * | 2022-06-23 | 2022-09-27 | 之江实验室 | Visual microreactor and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113828260B (en) | 2023-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3192786B1 (en) | Preparation method of sic porous ceramic material | |
| CN100460054C (en) | Porous membrane microstructure devices and methods of manufacture | |
| CN110922204B (en) | Preparation method of low-temperature sintered alumina ceramic membrane | |
| CN108261928A (en) | Pure silicon carbide ceramics membrane component and preparation method thereof | |
| CN104072141B (en) | The preparation method of a kind of silicon carbide honeycomb ceramics | |
| CN113828260A (en) | Manufacturing method and application of ceramic microreactor | |
| CN106390988B (en) | It is a kind of for doping type ozone catalyst based on regular ceramic honey comb carbon carrier of advanced treatment of industrial waste water and preparation method thereof | |
| CN112939580B (en) | Preparation method of ceramic filtering membrane | |
| CN106745673A (en) | A kind of micropore excessively stream ozone catalytic ceramic membrane and its methods for making and using same for Sewage advanced treatment | |
| CN102151560B (en) | Titanium dioxide photonic crystal film for photocatalytic degradation of organic matters | |
| CN106219724A (en) | Utilize charcoal absorption and the method for the catalysis persulfate orange II waste water from dyestuff of degraded | |
| CN108341671A (en) | Multichannel silicon carbide ceramics membrane component and preparation method thereof | |
| CN107376658A (en) | One kind is loaded with Ag TiO2PES milipore filters and its preparation method and application | |
| CN103721578A (en) | Multi-channel pure silicon carbide film with asymmetric structure and preparation method for multi-channel pure silicon carbide film | |
| CN111359450B (en) | Ceramic ultrafiltration membrane with efficient photocatalytic function and preparation method thereof | |
| CN108395252A (en) | Liquid-phase sintering multichannel silicon carbide ceramic support body and preparation method thereof | |
| CN109482190A (en) | A kind of foamed nickel supported zinc titanate catalysis material and preparation method thereof | |
| CN106007720A (en) | Silicon carbide composite zero-valent iron porous ceramics for sewage treatment and preparing method | |
| CN103752304A (en) | Method for preparing silicon-oxide-supported bismuth titanate photocatalyst | |
| CN111410547A (en) | Solid waste based ceramic catalytic membrane and preparation method and application thereof | |
| CN103962014B (en) | The manufacture method of the board-like ceramic integral membrane component of honeycomb bundle holes hollow | |
| KR101234490B1 (en) | Ceramics filter and manufacturing method thereby | |
| CN108264354A (en) | Multichannel silicon carbide ceramic support body and preparation method thereof | |
| CN106362768B (en) | A kind of honeycomb ceramic plate loads TiO2The preparation technology of the immobilized photochemical catalysts of-NCP | |
| CN112337411B (en) | Preparation method and application of metal organic gel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |