CN115055137A - Processing method of microreactor - Google Patents
Processing method of microreactor Download PDFInfo
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- CN115055137A CN115055137A CN202210932361.4A CN202210932361A CN115055137A CN 115055137 A CN115055137 A CN 115055137A CN 202210932361 A CN202210932361 A CN 202210932361A CN 115055137 A CN115055137 A CN 115055137A
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- transparent ceramic
- microreactor
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- ceramic microreactor
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- 238000003672 processing method Methods 0.000 title claims abstract description 10
- 239000000919 ceramic Substances 0.000 claims abstract description 116
- 239000000758 substrate Substances 0.000 claims abstract description 104
- 238000005498 polishing Methods 0.000 claims abstract description 33
- 238000005516 engineering process Methods 0.000 claims abstract description 31
- 238000005459 micromachining Methods 0.000 claims abstract description 27
- 238000000137 annealing Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000005260 corrosion Methods 0.000 claims abstract description 4
- 230000007797 corrosion Effects 0.000 claims abstract description 4
- 238000004321 preservation Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 33
- 239000002223 garnet Substances 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 claims description 15
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 claims description 15
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052771 Terbium Inorganic materials 0.000 claims description 14
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- 229910052596 spinel Inorganic materials 0.000 claims description 14
- 239000011029 spinel Substances 0.000 claims description 14
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 14
- 238000006073 displacement reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 230000003746 surface roughness Effects 0.000 claims description 8
- 238000002834 transmittance Methods 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000012530 fluid Substances 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 230000008569 process Effects 0.000 description 23
- FNCIDSNKNZQJTJ-UHFFFAOYSA-N alumane;terbium Chemical compound [AlH3].[Tb] FNCIDSNKNZQJTJ-UHFFFAOYSA-N 0.000 description 13
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- -1 magnesium aluminate Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention discloses a processing method of a micro-reactor, which comprises the following steps: step S1: taking transparent ceramic as a microreactor substrate; step S2: forming a modified pattern in the transparent ceramic microreactor substrate by using a femtosecond laser micromachining technology; step S3: forming a microchannel in the transparent ceramic microreactor substrate; step S4: polishing the microchannel by utilizing a microchannel polishing technology to obtain a transparent ceramic microreactor substrate with a smooth inner wall of the microchannel; step S5: and carrying out heat preservation and annealing treatment on the substrate of the transparent ceramic microreactor with the smooth inner wall of the microchannel to obtain the transparent ceramic microreactor. The invention adopts transparent ceramic as the substrate material of the microreactor, and simultaneously utilizes the femtosecond laser micromachining technology to form a microreaction channel in the transparent ceramic microreactor substrate. The prepared transparent ceramic microreactor can bear fluid pressure of more than 5Mpa and use temperature of-50 ℃ to 1500 ℃, and can bear acid, alkali and organic matter corrosion.
Description
Technical Field
The invention relates to the technical field of microreactors, in particular to a method for processing a microreactor.
Background
The microreactor is widely applied to the fields of chemistry, biology, materials, energy, bionics and the like. The micro-channels in the micro-reactor form a network, and controllable fluid penetrates through the network, so that the basic functions of biological and chemical experiments are realized. Generally, the micro-reactor adopts ceramics, metals, glass and the like with stable chemical properties and stable thermodynamic properties as matrix materials. Meanwhile, the micro-channel of the micro-reactor is formed by etching grooves on the surface of the substrate and sealing the substrate.
CN107376796B proposes a sapphire crystal as a micro reactor substrate, and a micro reaction channel is processed on the surface of the substrate, and then the micro reactor substrate is laminated and packaged to form a micro reactor. The method described in patent CN107376796B is also a common method for preparing a micro-reactor at present, but the processing method of the micro-reactor involves connection and packaging between substrates, the process is difficult, and high temperature of 2050 ℃ is required for sealing at most, and the failure of sealing between substrates will cause leakage of micro-channels of the micro-reactor.
Therefore, the invention provides a processing method of the microreactor.
Disclosure of Invention
The invention aims to provide a method for processing a microreactor, which solves the problems of the prior art in preparing the microreactor by laminated sealing, is simple to process and operate and meets the processing requirements of large scale and low cost.
The technical scheme adopted by the invention is as follows:
a method of fabricating a microreactor comprising the steps of:
step S1: taking transparent ceramic as a microreactor substrate;
step S2: forming a modified pattern in the transparent ceramic microreactor substrate by using a femtosecond laser micromachining technology;
step S3: pretreating the processed transparent ceramic microreactor substrate to form a microchannel in the transparent ceramic microreactor substrate;
step S4: polishing the microchannel by utilizing a microchannel polishing technology, and polishing the outer surface of the transparent ceramic microreactor substrate to obtain the transparent ceramic microreactor substrate with the smooth inner wall of the microchannel;
step S5: and (3) carrying out heat preservation and annealing treatment on the transparent ceramic microreactor substrate with the smooth inner wall of the microchannel to obtain the transparent ceramic microreactor.
Further, the transparent ceramic is a material having a transmittance in the visible light region and the near infrared region of more than 80% of any one of: alumina, yttria, yttrium aluminum garnet, terbium gallium garnet, or magnesium aluminum spinel.
Further, the laser center parameters adopted by the femtosecond laser micromachining technology in step S2 are as follows: the wavelength is 300-2000nm, the laser repetition frequency is more than or equal to 100KHz, the pulse width is less than or equal to 300fs, the laser power is more than or equal to 30mW, the maximum bearing capacity of the piezoelectric micro-displacement platform is more than or equal to 1kg, and the minimum motion variation of the piezoelectric micro-displacement platform on the Z axis is less than or equal to 100 nm.
Further, the step S3 specifically includes the following steps: soaking the processed transparent ceramic microreactor substrate in an acid-base corrosive liquid, and placing a container for containing the acid-base corrosive liquid in a temperature of 50-80 ℃, an ultrasonic frequency of not less than 20KHz and a power density of not less than 0.3W/cm 2 In the ultrasonic cleaning pool, after acid-base corrosion and ultrasonic water bath heating, a pattern area which is locally modified by a femtosecond laser micromachining technology is completely removed, and then the pattern area is repeatedly washed in a cleaning medium, so that a microchannel is formed in the substrate of the transparent ceramic microreactor.
Further, the acid-base corrosive liquid is any one of the following: aqua regia, hydrochloric acid, sulfuric acid, nitric acid, concentrated phosphoric acid, hydrofluoric acid, sodium hydroxide, potassium hydroxide, sodium bicarbonate or potassium bicarbonate.
Further, the cleaning medium is deionized water, ethanol or acetone.
Further, the temperature of the thermal annealing treatment in the step S5 is 1000-1600 ℃, and the time is 0.5-24 h.
Further, in the step S2, the transparent ceramic microreactor substrate is subjected to cutting, grinding, polishing and annealing before the femtosecond laser micromachining technology is utilized, so as to obtain the transparent ceramic microreactor substrate with the flatness of less than or equal to 0.1mm and the surface roughness Ra of less than 0.2 μm.
The invention has the beneficial effects that: the invention provides a processing method of a micro-reactor, which adopts transparent ceramic as a substrate material of the micro-reactor and simultaneously utilizes a femtosecond laser micro-processing technology to form a micro-reaction channel in the substrate of the transparent ceramic micro-reactor. The prepared transparent ceramic microreactor can bear the fluid pressure of more than 5Mpa and the use temperature of-50 ℃ to 1500 ℃, can bear acid-base and organic matter corrosion, and has the advantages of reducing danger and saving production cost in the fields of chemical industry, medicine, pesticide, fuel, explosive and the like. Particularly, phosgene, phosgenation, chlorination, nitration, fluorination, hydrogenation, diazotization, oxidation, amination, sulfonation, polymerization, alkylation, azotization and other exothermic reactions, and the raw materials are inflammable, explosive and even extremely toxic. The processing method of the micro-reactor provided by the invention can realize low-cost batch preparation of the transparent ceramic micro-reactor, and can promote green, safe and efficient chemical production when being applied to the chemical industry, thereby bringing great economic and social benefits.
Detailed Description
The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
Example 1:
step S1: the transparent yttria ceramics with the transmittance of more than 80 percent in a visible light region and a near infrared region is used as a micro-reactor substrate;
the size of the yttrium oxide transparent ceramic microreactor substrate is obtained by cutting, grinding, polishing and annealing the yttrium oxide transparent ceramic microreactor substrate: 200mm 20mm, flatness: 0.05mm and a surface roughness Ra <0.2 μm;
step S2: forming a modified pattern with the minimum diameter of 10 mu m in the inner part of the yttria transparent ceramic microreactor substrate by utilizing a femtosecond laser micromachining technology;
the femtosecond laser micromachining adopts the femtosecond laser with the center wavelength of 1064nm, the laser repetition frequency of 200kHz, the pulse width of 220fs and the laser power of 30-100mW, the scanning speed of 25 mu m/s, the maximum bearing capacity of the piezoelectric micro-displacement platform of 2Kg, and the minimum motion variation of the piezoelectric micro-displacement platform on the Z axis of 50 nm.
Step S3: pretreating the processed yttrium oxide transparent ceramic microreactor substrate to form a microchannel in the yttrium oxide transparent ceramic microreactor substrate;
soaking the yttrium oxide transparent ceramic microreactor substrate in concentrated phosphoric acid, and placing a container for containing the concentrated phosphoric acid at 70 ℃, ultrasonic frequency of 20KHz and power density of 0.3W/cm 2 In the ultrasonic cleaning pool, after concentrated phosphoric acid is combined with ultrasonic water bath heating, a pattern area which is locally modified by a femtosecond laser micromachining technology is completely removed, and then the pattern area is repeatedly washed in cleaning medium deionized water, so that a microchannel is formed in the inner part of the yttrium oxide transparent ceramic microreactor substrate.
Step S4: polishing the microchannel by utilizing a microchannel polishing technology, and polishing the outer surface of the yttria transparent ceramic microreactor substrate to obtain the yttria transparent ceramic microreactor substrate with a smooth inner wall of the microchannel;
step S5: and placing the yttrium oxide transparent ceramic microreactor substrate with the smooth inner wall of the microchannel in a high-temperature vacuum furnace at 1500 ℃ for annealing treatment for 5 hours to obtain the yttrium oxide transparent ceramic microreactor.
The yttrium oxide transparent ceramic microreactor is applied to continuous manufacturing of azide reaction medicaments, the occupied area required by the realization of the same capacity is reduced to one tenth of that of the traditional process, the reaction time is reduced to one hundredth of that of the traditional process, and the utilization rate of raw materials is improved by two times compared with that of the traditional process.
Example 2:
step S1: taking yttrium aluminum garnet transparent ceramics with transmittance exceeding 80% in a visible light region and a near infrared region as a microreactor substrate;
the size of the yttrium aluminum garnet transparent ceramic microreactor substrate is obtained by cutting, grinding, polishing and annealing the yttrium aluminum garnet transparent ceramic microreactor substrate: 100mm 20mm, flatness: 0.05mm and a surface roughness Ra <0.2 μm;
step S2: forming a modified pattern with the minimum diameter of 10 mu m in the yttrium aluminum garnet transparent ceramic microreactor substrate by using a femtosecond laser micromachining technology;
the femtosecond laser adopted for the femtosecond laser micromachining has the central wavelength of 2000nm, the repetition frequency of 300kHz, the pulse width of 200fs, the laser power of 50-500mW, the scanning speed of 20 mu m/s, the maximum bearing capacity of the piezoelectric micro-displacement platform of 2Kg and the minimum motion variation of the piezoelectric micro-displacement platform on the Z axis of 50 nm.
Step S3: pretreating the processed yttrium aluminum garnet transparent ceramic microreactor substrate to form a microchannel in the yttrium aluminum garnet transparent ceramic microreactor substrate;
soaking the yttrium aluminum garnet transparent ceramic microreactor substrate in concentrated phosphoric acid, and placing a container for containing the concentrated phosphoric acid at 75 ℃, ultrasonic frequency of 30KHz and power density of 1W/cm 2 In the ultrasonic cleaning pool, after concentrated phosphoric acid is combined with ultrasonic water bath for heating, a pattern area which is locally modified by a femtosecond laser micromachining technology is completely removed, and then the pattern area is repeatedly washed in cleaning medium ethanol, so that a microchannel is formed in the inner part of the yttrium aluminum garnet transparent ceramic microreactor substrate.
Step S4: polishing the microchannel by utilizing a microchannel polishing technology, and polishing the outer surface of the yttrium aluminum garnet transparent ceramic microreactor substrate to obtain the yttrium aluminum garnet transparent ceramic microreactor substrate with a smooth inner wall of the microchannel;
step S5: and placing the yttrium aluminum garnet transparent ceramic microreactor substrate with the smooth inner wall of the microchannel in a high-temperature vacuum furnace at 1200 ℃ for annealing treatment for 6 hours to obtain the yttrium aluminum garnet transparent ceramic microreactor.
The yttrium aluminum garnet transparent ceramic microreactor is applied to continuous crystallization synthesis of sulfonation reaction, the occupied area required by the realization of the same capacity is reduced to one fiftieth of the traditional process, the reaction time is reduced to one fiftieth of the traditional process, the utilization rate of raw materials is doubled compared with that of the traditional process, and the generation amount of waste liquid is reduced by half compared with that of the traditional process.
Example 3:
step S1: taking alumina transparent ceramics with transmittance exceeding 80% in a visible light region and a near infrared region as a microreactor substrate;
cutting, grinding, polishing and annealing the alumina transparent ceramic microreactor substrate to obtain the size of the alumina transparent ceramic microreactor substrate: 150mm 20mm, flatness: 0.1mm and a surface roughness Ra <0.2 μm;
step S2: forming a modified pattern with the minimum diameter of 10 mu m in the substrate of the aluminum oxide transparent ceramic microreactor by using a femtosecond laser micromachining technology;
the femtosecond laser micro-machining adopts the femtosecond laser with the central wavelength of 800nm, the repetition frequency of 300kHz, the pulse width of 200fs, the laser power of 50-500mW, the scanning speed of 20μm/s, the maximum load bearing capacity of the piezoelectric micro-displacement platform of 2Kg and the minimum motion variation of the Z axis of 50 nm.
Step S3: pretreating the processed aluminum oxide transparent ceramic microreactor substrate to form a microchannel in the aluminum oxide transparent ceramic microreactor substrate;
soaking the substrate of the alumina transparent ceramic microreactor in concentrated phosphoric acid, and placing a container for containing the concentrated phosphoric acid at the temperature of 80 ℃, the ultrasonic frequency of 40KHz and the power density of 0.5W/cm 2 In the ultrasonic cleaning pool, after concentrated phosphoric acid is combined with ultrasonic water bath heating, a pattern area which is locally modified by a femtosecond laser micromachining technology is completely removed, and then the pattern area is repeatedly washed in cleaning medium acetone, so that a microchannel is formed in the inner part of the aluminum oxide transparent ceramic microreactor substrate.
Step S4: polishing the microchannel by utilizing a microchannel polishing technology, and polishing the outer surface of the alumina transparent ceramic microreactor substrate to obtain the alumina transparent ceramic microreactor substrate with a smooth inner wall of the microchannel;
step S5: and placing the alumina transparent ceramic microreactor substrate with the smooth inner wall of the microchannel in a high-temperature vacuum furnace at 1500 ℃ for annealing treatment for 10 hours to obtain the alumina transparent ceramic microreactor.
The aluminum oxide transparent ceramic microreactor is applied to nitration reaction, the occupied area required by the realization of the same capacity is reduced to one tenth of that of the traditional process, the reaction time is reduced to one tenth of that of the traditional process, and the utilization rate of raw materials is improved by two times compared with that of the traditional process.
Example 4:
step S1: the magnesium aluminate spinel transparent ceramic with transmittance of more than 80% in a visible light region and a near infrared region is used as a micro-reactor substrate;
cutting, grinding, polishing and annealing the substrate of the magnesia-alumina spinel transparent ceramic microreactor to obtain the substrate of the magnesia-alumina spinel transparent ceramic microreactor with the following dimensions: 150mm 20mm, flatness: 0.05mm and a surface roughness Ra <0.2 μm;
step S2: forming a modified pattern with the minimum diameter of 10 mu m in the substrate of the magnesia-alumina spinel transparent ceramic microreactor by utilizing a femtosecond laser micromachining technology;
the femtosecond laser micro-machining adopts the femtosecond laser with the central wavelength of 1500nm, the repetition frequency of 300kHz, the pulse width of 200fs, the laser power of 50-500mW, the scanning speed of 20μm/s, the maximum load bearing capacity of the piezoelectric micro-displacement platform of 2Kg and the minimum motion variation of the Z axis of 50 nm.
Step S3: pretreating the processed magnesia alumina spinel transparent ceramic microreactor substrate to form a microchannel in the substrate;
soaking the substrate of the magnesia-alumina spinel transparent ceramic microreactor in sodium hydroxide, and placing a container for containing the sodium hydroxide at the temperature of 75 ℃, the ultrasonic frequency of 40KHz and the power density of 0.5W/cm 2 In the ultrasonic cleaning pool, after heating by combining sodium hydroxide and ultrasonic water bath, a pattern area which is locally modified by a femtosecond laser micromachining technology is completely removed, and then the pattern area is repeatedly washed in cleaning medium deionized water, so that a microchannel is formed in the substrate of the magnesia-alumina spinel transparent ceramic microreactor.
Step S4: polishing the microchannel by utilizing a microchannel polishing technology, and polishing the outer surface of the magnesia alumina spinel transparent ceramic microreactor substrate to obtain the magnesia alumina spinel transparent ceramic microreactor substrate with a smooth inner wall of the microchannel;
step S5: and placing the substrate of the magnesia-alumina spinel transparent ceramic microreactor with smooth inner wall of the microchannel in a muffle furnace at 1000 ℃ for annealing treatment in air atmosphere for 10 hours to obtain the magnesia-alumina spinel transparent ceramic microreactor.
The magnesium aluminate spinel transparent ceramic microreactor is applied to synthesis of a peroxide initiator, the occupied area required by the realization of the same capacity is reduced to one twentieth of that of the traditional process, the reaction time is reduced to one tenth of that of the traditional process, and the utilization rate of raw materials is doubled compared with that of the traditional process.
Example 5:
step S1: terbium aluminum garnet transparent ceramics with transmittance exceeding 80% in a visible light region and a near infrared region are used as microreactor substrates;
cutting, grinding, polishing and annealing the terbium aluminum garnet transparent ceramic microreactor substrate to obtain the size of the terbium aluminum garnet transparent ceramic microreactor substrate: 100mm 20mm, flatness: 0.01mm and a surface roughness Ra <0.1 μm;
step S2: forming a modified pattern with the minimum diameter of 10 mu m in the terbium aluminum garnet transparent ceramic microreactor substrate by using a femtosecond laser micromachining technology;
the femtosecond laser micro-processing adopts the femtosecond laser with the central wavelength of 380nm, the repetition frequency of 100kHz, the pulse width of 300fs, the laser power of 30-200mW, the scanning speed of 50 mu m/s, the maximum bearing capacity of the piezoelectric micro-displacement platform of 1Kg and the minimum motion variation of the Z axis of 100 nm.
Step S3: pretreating the processed terbium aluminum garnet transparent ceramic microreactor substrate to form a microchannel in the terbium aluminum garnet transparent ceramic microreactor substrate;
soaking the substrate of the transparent terbium aluminum garnet ceramic microreactor in hydrofluoric acid, and placing a container containing the hydrofluoric acid at 50 ℃, ultrasonic frequency of 30KHz and power density of 2W/cm 2 In the ultrasonic cleaning pool, after being heated by hydrofluoric acid and ultrasonic water bath, the pattern area which is locally modified by femtosecond laser micromachining technology is completely removed, and then the pattern area is repeatedly washed in cleaning medium ethanol, so that a microchannel is formed in the terbium aluminum garnet transparent ceramic microreactor substrate.
Step S4: polishing the microchannel by utilizing a microchannel polishing technology, and polishing the outer surface of the terbium aluminum garnet transparent ceramic microreactor substrate to obtain the terbium aluminum garnet transparent ceramic microreactor substrate with a smooth inner wall of the microchannel;
step S5: and (3) placing the terbium aluminum garnet transparent ceramic microreactor substrate with the smooth inner wall of the microchannel in a muffle furnace at 1000 ℃ for annealing treatment in air atmosphere for 24 hours to obtain the terbium aluminum garnet transparent ceramic microreactor.
The terbium aluminum garnet transparent ceramic microreactor is applied to chlorination reaction, the occupied area required by the realization of the same capacity is reduced to one twentieth of that of the traditional process, the reaction time is reduced to one tenth of that of the traditional process, the utilization rate of raw materials is doubled compared with that of the traditional process, and the generation amount of waste liquid is reduced by half compared with that of the traditional process.
Example 6:
step S1: terbium gallium garnet transparent ceramics with transmittance exceeding 80% in a visible light region and a near infrared light region are used as a micro-reactor substrate;
cutting, grinding, polishing and annealing the terbium gallium garnet transparent ceramic microreactor substrate to obtain the size of the terbium gallium garnet transparent ceramic microreactor substrate: 100mm 20mm, flatness: 0.01mm and a surface roughness Ra <0.1 μm;
step S2: forming a modified pattern with the minimum diameter of 10 mu m in the terbium gallium garnet transparent ceramic microreactor substrate by using a femtosecond laser micromachining technology;
the femtosecond laser micro-machining adopts the femtosecond laser with the central wavelength of 300nm, the repetition frequency of 76MHz, the pulse width of 300fs, the laser power of 30-500mW, the scanning speed of 40 μm/s, the maximum load bearing capacity of the piezoelectric micro-displacement platform of 1Kg and the minimum motion variation of the Z axis of 100 nm.
Step S3: pretreating the processed terbium gallium garnet transparent ceramic microreactor substrate to form a microchannel in the substrate;
soaking the substrate of the terbium gallium garnet transparent ceramic microreactor in hydrochloric acid, and placing a container for containing the hydrochloric acid at the temperature of 50 ℃, the ultrasonic frequency of 20KHz and the power density of 0.3W/cm 2 In the ultrasonic cleaning pool, after hydrochloric acid and ultrasonic water bath heating, a pattern area which is locally modified by a femtosecond laser micromachining technology is completely removed, and then the pattern area is repeatedly washed in cleaning medium acetone, so that a microchannel is formed in the substrate of the terbium gallium garnet transparent ceramic microreactor.
Step S4: polishing the microchannel by using a microchannel polishing technology, and polishing the outer surface of the terbium gallium garnet transparent ceramic microreactor substrate to obtain the terbium gallium garnet transparent ceramic microreactor substrate with a smooth inner wall of the microchannel;
step S5: and (3) placing the substrate of the terbium gallium garnet transparent ceramic microreactor with the smooth inner wall of the microchannel in a muffle furnace at 1600 ℃ for annealing treatment in an air atmosphere for 0.5 hour to obtain the terbium gallium garnet transparent ceramic microreactor.
The terbium gallium garnet transparent ceramic microreactor is applied to fluorination reaction, the occupied area required by the realization of the same capacity is reduced to one tenth of that of the traditional process, the reaction time is reduced to one tenth of that of the traditional process, the utilization rate of raw materials is improved by two times compared with that of the traditional process, and the generation amount of waste liquid is reduced by one half compared with that of the traditional process.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A processing method of a micro-reactor is characterized by comprising the following steps:
step S1: taking transparent ceramic as a microreactor substrate;
step S2: forming a modified pattern in the transparent ceramic microreactor substrate by using a femtosecond laser micromachining technology;
step S3: pretreating the processed transparent ceramic microreactor substrate to form a microchannel in the transparent ceramic microreactor substrate;
step S4: polishing the microchannel by utilizing a microchannel polishing technology, and polishing the outer surface of the transparent ceramic microreactor substrate to obtain the transparent ceramic microreactor substrate with the smooth inner wall of the microchannel;
step S5: and (3) carrying out heat preservation and annealing treatment on the transparent ceramic microreactor substrate with the smooth inner wall of the microchannel to obtain the transparent ceramic microreactor.
2. The method for processing a microreactor according to claim 1, wherein the transparent ceramic is any one of the following materials having a transmittance in the visible region and the near-infrared region exceeding 80%: alumina, yttria, yttrium aluminum garnet, terbium gallium garnet, or magnesium aluminum spinel.
3. The method for processing a microreactor as claimed in claim 1, wherein the femtosecond laser micromachining technique in step S2 uses the following laser center parameters: the wavelength is 300-2000nm, the laser repetition frequency is more than or equal to 100KHz, the pulse width is less than or equal to 300fs, the laser power is more than or equal to 30mW, the maximum bearing capacity of the piezoelectric micro-displacement platform is more than or equal to 1kg, and the minimum motion variation of the piezoelectric micro-displacement platform on the Z axis is less than or equal to 100 nm.
4. The method for processing a microreactor as claimed in claim 1, wherein the step S3 specifically comprises the steps of: soaking the processed transparent ceramic microreactor substrate in an acid-base corrosive liquid, and placing a container for containing the acid-base corrosive liquid in a temperature of 50-80 ℃, an ultrasonic frequency of not less than 20KHz and a power density of not less than 0.3W/cm 2 In the ultrasonic cleaning pool, after acid-base corrosion and ultrasonic water bath heating, the pattern area which is locally modified by the femtosecond laser micromachining technology is completely removed, and then the pattern area is repeatedly washed in a cleaning medium, so that the pattern area is cleanedAnd microchannels are formed inside the transparent ceramic microreactor substrate.
5. The microreactor processing method according to claim 4, wherein the acid-base corrosive liquid is any one of: aqua regia, hydrochloric acid, sulfuric acid, nitric acid, concentrated phosphoric acid, hydrofluoric acid, sodium hydroxide, potassium hydroxide, sodium bicarbonate or potassium bicarbonate.
6. The microreactor processing method of claim 4 wherein the cleaning medium is deionized water, ethanol or acetone.
7. The method for processing a microreactor as claimed in claim 1, wherein the temperature of the thermal annealing treatment in step S5 is 1000-1600 ℃ and the time is 0.5-24 h.
8. The method of claim 1, wherein in step S2, the transparent ceramic microreactor substrate is cut, ground, polished and annealed before the femtosecond laser micromachining technology is used, so as to obtain a transparent ceramic microreactor substrate with a flatness of 0.1mm or less and a surface roughness Ra of 0.2 μm or less.
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