CN116651136A - Micro chromatographic column for light hydrocarbon separation and preparation method thereof - Google Patents
Micro chromatographic column for light hydrocarbon separation and preparation method thereof Download PDFInfo
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 46
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 46
- 238000000926 separation method Methods 0.000 title claims abstract description 35
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000013148 Cu-BTC MOF Substances 0.000 claims abstract description 125
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 76
- 239000000463 material Substances 0.000 claims abstract description 56
- 230000000694 effects Effects 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims description 48
- 239000000843 powder Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 55
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract description 18
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- 238000004445 quantitative analysis Methods 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 5
- 238000004451 qualitative analysis Methods 0.000 abstract description 5
- 238000012216 screening Methods 0.000 abstract description 5
- -1 further Substances 0.000 abstract description 4
- 230000023077 detection of light stimulus Effects 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- MEKDPHXPVMKCON-UHFFFAOYSA-N ethane;methane Chemical compound C.CC MEKDPHXPVMKCON-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000012621 metal-organic framework Substances 0.000 description 7
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 239000000306 component Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000708 deep reactive-ion etching Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HOWJQLVNDUGZBI-UHFFFAOYSA-N butane;propane Chemical compound CCC.CCCC HOWJQLVNDUGZBI-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLNZHTHIPQGEMX-UHFFFAOYSA-N ethane propane Chemical compound CCC.CCC.CC.CC XLNZHTHIPQGEMX-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0407—Constructional details of adsorbing systems
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00111—Tips, pillars, i.e. raised structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00119—Arrangement of basic structures like cavities or channels, e.g. suitable for microfluidic systems
Abstract
The invention provides a micro chromatographic column for separating light hydrocarbon and a preparation method thereof, FG-HKUST-1 stationary phase of the micro chromatographic column is prepared by FG and HKUST-1, and the FG-HKUST-1 stationary phase is made of nonpolar material, besides having screening effect on C1-C4 light hydrocarbon, further, dispersion force exists between the nonpolar FG-HKUST-1 stationary phase and nonpolar light hydrocarbon, such as nonpolar methane and ethane, so that the nonpolar FG-HKUST-1 stationary phase has stronger retention capacity against nonpolar light hydrocarbon, thereby improving the separation degree of C1-C4 light hydrocarbon, especially aiming at light hydrocarbon with lower separation degree, great concentration difference and relatively close property, such as methane and ethane, thereby meeting the requirements for qualitative and quantitative analysis and detection of light hydrocarbon.
Description
Technical Field
The invention belongs to the field of micro-electromechanical systems, and relates to a micro-chromatographic column for light hydrocarbon separation and a preparation method thereof.
Background
As a common analysis means, gas chromatography has been widely used in the fields of petrochemical industry, drug detection, energy exploration, environmental monitoring, and the like. The core component of the gas chromatograph is a chromatographic column for separating the mixed gas sample, and in the whole test system, the chromatographic column plays a role in separating the mixed gas, and the performance of the chromatographic column directly influences the analysis effect of the whole analysis instrument. The separation effect of the chromatographic column mainly depends on the stationary phase coated on the inner surface of the channel, and the adsorption and desorption capacities of different gases are different, so that the flowing speeds of different gas components to be detected in the channel are different, and finally, the different gas components reach the outlet of the chromatographic column at different times, thereby realizing the separation of mixed gases.
Because the traditional chromatographic column needs a larger oven for heating and keeping the temperature stable, the whole chromatographic column has large volume and high power consumption, and is difficult to meet the requirements of real-time separation detection. Therefore, the key to the overall miniaturization of the chromatograph is the miniaturization of the chromatographic column.
Since the end of the 70 s of the 20 th century, attempts have been made to fabricate microchromatography column chips on silicon wafers by etching/etching using microelectromechanical techniques. In order to improve the separation efficiency of the silicon-based micro-chromatographic column, researchers have carried out an optimal design on the geometry of the micro-chromatographic column and have made important progress, wherein, in order to further increase the internal surface area of the chromatographic column, the researchers design a micro-column array in the channel of the micro-chromatographic column, namely a so-called semi-packed column structure, which further improves the separation performance of the micro-chromatographic column; on the other hand, the stationary phase is also another key factor affecting the separation effect of the micro-chromatography column, wherein materials such as polydimethylsiloxane, alumina nanoparticles, mesoporous silica, etc. have been used as the stationary phase of the silicon-based micro-chromatography column. However, in the separation of light hydrocarbons, especially in the separation of methane-ethane, the separation degree is low, and the difference between the retention times of methane-ethane is short, when the methane concentration in an actual sample is far higher than that of ethane (such as natural gas, etc.), the methane peak may flood the ethane peak, which results in the failure to perform qualitative and quantitative analysis and detection on the light hydrocarbons such as methane-ethane.
Therefore, it is necessary to provide a micro-chromatographic column for light hydrocarbon separation and a preparation method thereof.
Disclosure of Invention
In view of the above drawbacks of the prior art, an object of the present invention is to provide a micro-chromatographic column for light hydrocarbon separation and a preparation method thereof, which are used for solving the problem that the micro-chromatographic column in the prior art is difficult to effectively separate light hydrocarbons.
To achieve the above and other related objects, the present invention provides a microcohromatography column for light hydrocarbon separation, comprising:
a substrate;
a microchannel located in the substrate, the microchannel having a first port and a second port;
the micro-columns are positioned in the micro-channels, n rows of the micro-columns are arranged at intervals in the width direction of the micro-channels, and m rows of the micro-columns are arranged at intervals in the extending direction of the micro-channels so as to form an n multiplied by m micro-column array;
the cover plate is positioned on the surface of the substrate and covers the micro-channel to form a closed micro-channel;
an FG-HKUST-1 stationary phase covering the closed microchannel inner surface, the material forming the FG-HKUST-1 stationary phase comprising Fluorinated Graphene (FG) and metal-organic framework (MOF) material HKUST-1, the FG-HKUST-1 stationary phase having a sieving effect, and the FG-HKUST-1 stationary phase being a non-polar material.
Optionally, the light hydrocarbon comprises C1-C4 alkane.
Optionally, the operating temperature of the microchromatography column is below 300 ℃.
Optionally, the microcolumn includes an elliptical microcolumn or a circular microcolumn, and when the microcolumn is an elliptical microcolumn, a major axis direction of the elliptical microcolumn is parallel to an extension direction of the microchannel, and a minor axis direction of the elliptical microcolumn is parallel to a width direction of the microchannel.
Optionally, the cover plate comprises a glass cover plate, a silicon cover plate, or a ceramic cover plate.
Optionally, the micro-channel comprises a profile that includes one of serpentine, polyline, U-shaped, and spiral extensions.
The invention also provides a preparation method of the micro chromatographic column for light hydrocarbon separation, which comprises the following steps:
providing a substrate, and forming a patterned mask layer on the surface of the substrate;
etching the substrate based on the patterned mask layer to form a micro-channel and micro-columns in the substrate, wherein the micro-channel is provided with a first port and a second port, the micro-columns are positioned in the micro-channel, n columns of the micro-columns are arranged at intervals in the width direction of the micro-channel, and m rows of the micro-columns are arranged at intervals in the extending direction of the micro-channel so as to form an n multiplied by m micro-column array;
providing a cover plate, and bonding the cover plate to the surface of the substrate to cover the micro-channel to form a closed micro-channel;
forming an FG-HKUST-1 stationary phase, the FG-HKUST-1 stationary phase covering the closed microchannel inner surface, the material forming the FG-HKUST-1 stationary phase comprising Fluorinated Graphene (FG) and metal-organic framework (MOF) material HKUST-1, the FG-HKUST-1 stationary phase having a sieving effect, and the FG-HKUST-1 stationary phase being a non-polar material.
Optionally, the step of forming the FG-HKUST-1 stationary phase comprises:
mixing FG-HKUST-1 powder with a solvent to prepare FG-HKUST-1 solution;
injecting the FG-HKUST-1 solution into the closed microchannel from the first port and exiting through the second port to coat FG-HKUST-1 material in the closed microchannel;
an aging treatment is performed to convert the FG-HKUST-1 material into an FG-HKUST-1 stationary phase that covers the inner surface of the closed microchannel.
Optionally, the step of preparing the FG-HKUST-1 powder comprises:
placing FG powder in an N, N-Dimethylformamide (DMF) solvent, performing ultrasonic dispersion and standing, and collecting supernatant;
in Cu (NO) 3 ) 2 ·3H 2 O powder and trimesic acid (H) 3 Adding dimethyl sulfoxide (DMSO) solvent into BTC) powder, and performing ultrasonic dispersion and dissolution to obtain a mixed solution;
on CH 3 Adding the supernatant and the mixed solution into the OH solution, stirring and centrifugally separating to obtain a lower layer solid;
by CH 3 Washing with OH solution, and drying to obtain FG-HKUST-1 powder.
Optionally, after bonding the cover plate and before forming the FG-HKUST-1 stationary phase, a dicing step is further included.
As described above, according to the micro chromatographic column for light hydrocarbon separation and the preparation method thereof, FG and HKUST-1 are adopted to prepare FG-HKUST-1 stationary phase of the micro chromatographic column, and the FG-HKUST-1 stationary phase is made of nonpolar materials, so that besides the screening effect on the light hydrocarbons of C1-C4, further, dispersion force exists between the nonpolar FG-HKUST-1 stationary phase and the nonpolar light hydrocarbons, such as nonpolar methane and ethane, so that the nonpolar FG-HKUST-1 stationary phase has stronger retention capacity relative to the nonpolar light hydrocarbons, and the separation degree of the light hydrocarbons of C1-C4 can be improved, particularly, the requirements of qualitative and quantitative analysis and detection on the light hydrocarbons, such as methane and ethane, can be met.
Drawings
FIG. 1 shows a flow chart of a process for preparing a micro-chromatography column in an embodiment of the invention.
Fig. 2 to 5 are schematic views showing the structures obtained in the steps of preparing a microcomprhromatography column according to the embodiment of the present invention.
FIG. 6 shows a scanning electron microscope image of a microcolumn in an embodiment of the present invention.
Fig. 7 is an enlarged schematic top view of area a of fig. 6.
FIGS. 8a and 8b are schematic views showing a process apparatus in preparing FG-HKUST-1 stationary phase in accordance with an embodiment of the present invention.
FIG. 9 shows a graph comparing pore size distribution of FG-HKUST-1 material and HKUST-1 material in examples of the present invention.
FIG. 10 is a graph showing the results of thermogravimetric analysis of FG-HKUST-1 material in an example of the present invention.
FIG. 11 is a graph showing the results of light hydrocarbon separation tests performed on a microchromatography column in an embodiment of the present invention.
Description of element reference numerals
100. Substrate and method for manufacturing the same
110. Microchannel side wall
200. Mask layer
300. Micro-channel
310. First port of microchannel
400. Microcolumn
500. Cover plate
600. Closed microchannel
610. Closed microchannel inner surface
700 FG-HKUST-1 stationary phase
1. High-pressure air source
2. Pressure bottle
3. Stationary phase suspension
4. Adapter
5. Micro chromatographic column
6. Capillary tube
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
As described in detail in the embodiments of the present invention, the cross-sectional view of the device structure is not partially enlarged to a general scale for convenience of explanation, and the schematic drawings are only examples, which should not limit the scope of the present invention. In addition, the three-dimensional dimensions of length, width and depth should be included in actual fabrication.
For ease of description, spatially relative terms such as "under", "below", "beneath", "above", "upper" and the like may be used herein to describe one element or feature's relationship to another element or feature as illustrated in the figures. It will be understood that these spatially relative terms are intended to encompass other orientations of the device in use or operation in addition to the orientation depicted in the figures, including embodiments in which the first and second features are formed in direct contact, as well as embodiments in which additional features are formed between the first and second features, such that the first and second features may not be in direct contact, and further, when a layer is referred to as being "between" two layers, it may be the only layer between the two layers, or there may be one or more intervening layers.
It should be noted that, the illustrations provided in the present embodiment merely illustrate the basic concept of the present invention by way of illustration, and only the components related to the present invention are shown in the drawings and are not drawn according to the number, shape and size of the components in actual implementation, and the form, number and proportion of each component in actual implementation may be changed at will, and the layout of the components may be more complex.
As shown in fig. 1, the present embodiment provides a method for preparing a micro-chromatographic column, which includes the following steps:
s1: providing a substrate, and forming a patterned mask layer on the surface of the substrate;
s2: etching the substrate based on the patterned mask layer to form a micro-channel and micro-columns in the substrate, wherein the micro-channel is provided with a first port and a second port, the micro-columns are positioned in the micro-channel, n columns of the micro-columns are arranged at intervals in the width direction of the micro-channel, and m rows of the micro-columns are arranged at intervals in the extending direction of the micro-channel so as to form an n multiplied by m micro-column array;
s3: providing a cover plate, and bonding the cover plate to the surface of the substrate to cover the micro-channel to form a closed micro-channel;
s4: forming an FG-HKUST-1 stationary phase, the FG-HKUST-1 stationary phase covering the closed microchannel inner surface, the material forming the FG-HKUST-1 stationary phase comprising FG (fluorinated graphene) and a metal-organic framework Material (MOF) HKUST-1, the FG-HKUST-1 stationary phase having a sieving effect, and the FG-HKUST-1 stationary phase being a non-polar material.
According to the embodiment, the FG-HKUST-1 stationary phase of the micro chromatographic column is prepared by adopting the FG material and the HKUST-1 material, and the FG-HKUST-1 stationary phase is made of a nonpolar material, so that besides the screening effect on the C1-C4 light hydrocarbons, further, dispersion force exists between the nonpolar FG-HKUST-1 stationary phase and the nonpolar light hydrocarbons, such as nonpolar methane and ethane, so that the nonpolar FG-HKUST-1 stationary phase has stronger retention capacity on the nonpolar light hydrocarbons, and the separation degree of the C1-C4 light hydrocarbons can be improved, particularly for the light hydrocarbons with lower separation degree, great concentration difference and relatively close properties, such as methane and ethane, and the requirements on qualitative and quantitative analysis and detection of the light hydrocarbons can be met.
Referring to fig. 2 to 7, the structure of the micro-chromatography column and the preparation thereof will be described with reference to the accompanying drawings. Fig. 6 is a schematic diagram illustrating a scanning electron microscope of the microchromatography column formed in the present embodiment, fig. 2 and 3 are schematic diagrams showing a partially enlarged cross-sectional structure of a region a taken along C-C' in fig. 6, fig. 7 is a schematic diagram showing a top-view enlarged structure of a region a in fig. 6, fig. 4 is a schematic diagram showing a cross-sectional structure of the microchromatography column with a cover plate, and fig. 5 is a schematic diagram showing a cross-sectional structure of the microchromatography column after forming the FG-HKUST-1 stationary phase.
First, referring to fig. 1 and 2, step S1 is performed to provide a substrate 100, and a patterned mask layer 200 is formed on a surface of the substrate 100.
As an example, the substrate 100 may include a silicon substrate, a glass substrate, or a ceramic substrate; the mask layer 200 may include one or a combination of a silicon oxide mask layer, a silicon nitride mask layer, and a photoresist mask layer.
Specifically, the types of the substrate 100 and the mask layer 200 are not limited to this, and may be selected according to the need, in this embodiment, a silicon substrate is used as the substrate 100, and a photoresist mask layer covering the substrate 100 is used as the mask layer 200, but is not limited to this.
As an example, forming the patterned mask layer 200 on the surface of the substrate 100 may include the steps of:
forming the photoresist mask layer on the surface of the substrate 100;
the photoresist mask layer is subjected to patterning treatment by adopting a photoetching and etching process to obtain a photoresist etching window, and the shape and the position of the micro-channel 300 and the micro-column 400 which are to be formed later in fig. 3 can be defined through the photoresist etching window.
Next, referring to fig. 1, 3 and 6, step S2 is performed to etch the substrate 100 based on the patterned mask layer 200 to form the micro-channel 300 and the micro-pillars 400 in the substrate 100, wherein the micro-channel 300 has a first port 310 and a second port (not shown), the micro-pillars 400 are located in the micro-channel 300, and n columns of the micro-pillars 400 are arranged at intervals in the width direction of the micro-channel 300, and m rows of the micro-pillars 400 are arranged at intervals in the extending direction of the micro-channel 300 to form an n×m micro-pillar array.
Specifically, in the present embodiment, the exposed substrate 100 is etched based on a Deep Reactive Ion Etching (DRIE) technique to form the micro-channel 300 and the micro-column 400 in the substrate 100, but the etching method is not limited thereto, and may be adaptively selected according to requirements.
As an example, the micro-pillars 400 include elliptical micro-pillars or circular micro-pillars, and when the micro-pillars 400 employ elliptical micro-pillars, a major axis direction of the elliptical micro-pillars is parallel to an extending direction of the micro-channels, and a minor axis direction of the elliptical micro-pillars is parallel to a width direction of the micro-channels.
In particular, in this embodiment, it is preferable that the microcolumn 400 is an elliptical microcolumn, and the n×m elliptical microcolumn array located in the microchannel 300 can greatly reduce the area of the "quasi-zero flow velocity zone" formed after the microcolumn, so that a uniform stationary phase can be coated on the microcolumn 400 later, and the flow velocity distribution in the column is uniform.
Referring to fig. 7, in the present embodiment, the width of the microchannel 300 is w, the effective width of the microchannel 300 is d, n is 4, 3 sub-microchannels with the width S are formed in the microchannel 300, and 2 sub-microchannels with the width S, that is, d=3s+2s, in fact, the number of columns, the number of rows, the size, etc. of the elliptic micro-columns may be selected according to practical needs. The number of columns n and m of the elliptic micro-columns, the length q of the minor axis and the length p of the major axis of the elliptic micro-columns, the spacing S, s and the spacing t, etc. in the micro-channel 300 can be selected according to the need, and are not described herein. Wherein, the relation of q= (w-d)/n is preferable to adjust the short axis length q of the elliptical micro-column while increasing the number of the elliptical micro-column, so as to effectively increase the column inner surface area to improve the separation performance of the micro-chromatographic column while maintaining the width w of the micro-channel 300 and the effective width d of the micro-channel 300, and effectively solve the problem of the increase of the column front pressure caused by the increase of the number of the micro-column, so that the micro-chromatographic column can maintain lower column front pressure while effectively increasing the surface area, thereby improving the efficacy of the micro-chromatographic column, reducing the burden of an air supply system, being beneficial to portable application and having wide application prospect.
As an example, the adjacent n columns of the micro pillars 400 are equally spaced in the width direction along the micro channel 300 to reduce process complexity; or in the width direction along the micro channel 300, the n columns of micro columns can be arranged to have different intervals according to the requirement, so that the flow velocity distribution in the columns is further uniform, and the problem of uneven flow velocity of carrier gas is relieved.
As an example, the spacing S of adjacent n columns of the micro-pillars 400 is smaller than the spacing S between the micro-pillars 400 and the micro-channel sidewall 110 at the edges, i.e., S > S, in the width direction of the micro-channel 300 to provide a uniform flow rate in the micro-channel 300.
As an example, the micro-channel 300 may be formed to extend in a serpentine shape, although in other examples, the micro-channel 300 may be formed to extend in any manner within the substrate 100, such as a fold line extension, a U-shaped extension, a spiral extension, etc., without limitation.
Next, referring to fig. 1 and 4, step S3 is performed to provide a cover plate 500, and the cover plate 500 is bonded to the surface of the substrate 100 to cover the micro-channel 300, thereby forming a closed micro-channel 600.
By way of example, the cover plate 500 may comprise a glass cover plate, a silicon cover plate, or a ceramic cover plate, wherein the cover plate 500 is preferably the same material as the substrate 100 to facilitate the formation of a uniform stationary phase in the closed microchannel 600.
Specifically, referring to fig. 4, the cover plate 500 may be bonded to the surface of the substrate 100 using an anodic bonding process, wherein the bonding process conditions may be selected as desired, and are not excessively limited herein.
As an example, if a plurality of independent micro chromatographic columns are formed in the substrate 100, after the cover plate 500 is bonded to the surface of the substrate 100, the bonded structure may be diced to obtain a plurality of micro chromatographic columns, so as to improve the production efficiency. Then, capillaries may be installed at the first port 310 of the prepared microchannel 300, including an inlet end and an outlet end (not shown), respectively, as shown in fig. 8a and 8b, to serve as connection ends with external air channels, which will not be described herein.
Next, referring to fig. 1 and 5, step S4 is performed to form an FG-HKUST-1 stationary phase 700, the FG-HKUST-1 stationary phase 700 covering the closed microchannel inner surface 610, the material forming the FG-HKUST-1 stationary phase 700 comprising the FG material and the HKUST-1 material, the FG-HKUST-1 stationary phase 700 having a sieving effect, and the FG-HKUST-1 stationary phase 700 being a non-polar material.
Specifically, a comparison of pore size distribution of FG-HKUST-1 material to HKUST-1 material is illustrated with reference to FIG. 9. HKUST-1 material is a copper-based material with a variety of pore sizes including 0.6nm, 0.69nm and 0.9nm. FG-HKUST-1 materials still have a variety of size pore sizes, including 0.69nm, 0.9nm and small amounts of pore sizes greater than 1nm, with 0.69nm, 0.9nm pore sizes from HKUST-1 and pore sizes greater than 1nm from, for example, slit pores formed between HKUST-1 and FG. Since the molecular kinetic diameters of methane, ethane, propane and butane are respectively 0.38nm, 0.40nm, 0.42nm and 0.43nm, which are smaller than the characteristic pore diameters of FG-HKUST-1 materials, FG-HKUST-1 materials still have screening effect of HKUST-1 materials for C1-C4 light hydrocarbons. More importantly, the HKUST-1 is a polar material, the FG-HKUST-1 is a nonpolar material, and dispersion force exists between nonpolar methane and ethane molecules and nonpolar FG-HKUST-1, namely, the FG-HKUST-1 has stronger retention capacity on methane and ethane compared with the polar metal-organic framework HKUST-1 material, so that the separation of methane and ethane can be improved.
Wherein, FG-HKUST-1 material is compounded by FG material and HKUST-1 material, and the synthesis of FG-HKUST-1 powder can include the following steps:
placing FG powder in DMF (N, N-dimethylformamide) solvent, performing ultrasonic dispersion and standing, and collecting supernatant;
in Cu (NO) 3 ) 2 ·3H 2 O powder and H 3 Adding DMSO (dimethyl sulfoxide) solvent into BTC (trimesic acid) powder, and performing ultrasonic dispersion and dissolution to obtain a mixed solution;
on CH 3 Adding the supernatant and the mixed solution into the OH solution, stirring and centrifugally separating to obtain a lower layer solid;
by CH 3 Washing with OH solution, and drying to obtain FG-HKUST-1 powder.
The preparation of the FG-HKUST-1 powder may include the following specific steps, it should be noted that the following description is only an example, and the preparation of the FG-HKUST-1 powder is described, but the specific operation procedure, process, material, etc. are not limited thereto, and the following steps may be adaptively performed:
(1) Sequentially adding 15mL of DMF and 0.2g of FG powder into a glass bottle, carrying out ultrasonic treatment for 30min to obtain dispersed multilayer fluorinated graphene suspension, standing for 30min, and collecting supernatant;
(2) 1.22g Cu (NO) was weighed out 3 ) 2 ·3H 2 O and 0.58. 0.58g H 3 Putting BTC into a beaker, adding 5g of DMSO solvent, and performing ultrasonic treatment for 10min to dissolve the BTC;
(3) Into a Erlenmeyer flask was added 50mL CH 3 OH (methanol) and the collected supernatant, slowly dripping the solution in the beaker in the step (2) into a conical flask, and putting a magnet into the conical flask to stir for 24 hours to obtain a blue-green solution;
(4) Centrifuging the above blue-green solution with high speed centrifuge to obtain lower solid, and using CH 3 And (3) washing 3 times by OH, and finally drying in an oven at 80 ℃ for 12 hours to obtain blue-green solid FG-HKUST-1 powder.
As an example, the step of forming the FG-HKUST-1 stationary phase 700 may include:
mixing FG-HKUST-1 powder with a solvent to prepare FG-HKUST-1 solution;
injecting the FG-HKUST-1 solution into the closed micro-channel 600 from the first port 310 and discharging through the second port to coat FG-HKUST-1 material in the closed micro-channel 600;
an aging treatment is performed to convert the FG-HKUST-1 material into FG-HKUST-1 stationary phase 700 that covers the closed microchannel inner surface 610.
Referring to fig. 8a and 8b, it should be noted that the following description is given for forming the FG-HKUST-1 stationary phase 700 by way of example only, but the specific operation procedure, process, material, etc. are not limited thereto, and are specifically as follows:
micro-chromatography column coating pretreatment: the closed micro channel of the micro chromatographic column 5 is cleaned by alcohol/acetone and the like, and some impurities inside the micro chromatographic column 5 are removed.
Stationary phase coating: 20mg of FG-HKUST-1 powder is weighed and added into a pressure bottle 2 filled with 5mL of alcohol, and ultrasonic treatment is carried out at room temperature for not less than 10min, so as to obtain a stationary phase suspension 3 of FG-HKUST-1. According to FIG. 8a, one end of a pressure bottle 2 is connected with a high-pressure air source 1, such as nitrogen, helium or air (2.5 Mpa), the other end of the pressure bottle 2 is connected with one port of a micro chromatographic column 5 through an adapter 4, the other end of the micro chromatographic column 5 is suspended, a stationary phase suspension 3 in the pressure bottle 2 is pressed into a closed micro channel of the micro chromatographic column 5 by the high-pressure air source 1, after the liquid column completely passes through the other port of the micro chromatographic column 5, the high-pressure air source 1 is closed, the pressure bottle 2 is removed, nitrogen (or helium or air) with 0.2Mpa is used for purging, according to FIG. 8b, residual liquid in the closed micro channel of the micro chromatographic column 5 is removed, and then the micro chromatographic column 5 with the inner wall coated with FG-HKUST-1 stationary phase is obtained after aging for 5 hours at 120 ℃.
By way of example, the light hydrocarbons include C1-C4 alkanes, especially methane-ethane.
Specifically, when the prepared micro-chromatographic column is used for separating C1-C4 alkane, the separation effect is as shown in figure 11, and the chromatographic column is used for realizing the baseline separation of methane (volume concentration of 20%), ethane (volume concentration of 0.2%), propane (volume concentration of 0.2%) and butane (volume concentration of 0.2%). The concentration of methane and ethane are difficult to separate, but the retention time difference of the methane and the ethane is as high as 1.11min, and the separation degree of the methane-ethane can be as high as 9.18, so that the condition that the methane peak floods the ethane peak when the concentration of the methane-ethane is greatly different can be effectively avoided by using the chromatographic column. In addition, the separation degree of ethane-propane is 13.93, the separation degree of propane-butane is 7.80, and the separation degree required by quantitative analysis is generally not less than 1.5, so the quantitative analysis of C1-C4 light hydrocarbons can be carried out by using the chromatographic column, and particularly the nonpolar FG-HKUST-1 stationary phase 700 can improve the separation of the two light hydrocarbons with low separation degree, greatly different concentration and relatively close property of nonpolar methane-ethane.
As an example, the operating temperature of the microchromatography column is below 300 ℃.
In particular, referring to FIG. 10, which illustrates the thermogravimetric analysis of FG-HKUST-1 material, FG-HKUST-1 material should have a safe operating temperature of no greater than 300℃as a stationary phase material, mainly because H when the temperature is greater than 300 ℃ 3 BTC (trimesic acid) will be lost from the structure and thus the framework structure of FG-HKUST-1 will begin to collapse. Therefore, the operating temperature of the microcolumn is preferably 300 ℃ or less, such as 200 ℃ and 150 ℃.
Referring to fig. 5 to 7, the present embodiment further provides a micro-chromatography column, which includes:
a substrate 100;
a microchannel 300, the microchannel 300 being located in the substrate 100, the microchannel 300 having a first port 310 and a second port (not shown);
a micro-column 400, wherein the micro-column 400 is located in the micro-channel 300, and includes n columns of the micro-columns 400 arranged at intervals in a width direction of the micro-channel 300, and includes m rows of the micro-columns 400 arranged at intervals in an extending direction of the micro-channel 300, so as to form an n×m micro-column array;
a cover plate 500, wherein the cover plate 500 is positioned on the surface of the substrate 100 and covers the micro-channel 300 to form a closed micro-channel 600;
FG-HKUST-1 stationary phase 700, FG-HKUST-1 stationary phase 700 covers the closed microchannel inner surface 610, materials forming the FG-HKUST-1 stationary phase 700 include FG and HKUST-1, the FG-HKUST-1 stationary phase 700 has a sieving effect, and the FG-HKUST-1 stationary phase 700 is a nonpolar material.
By way of example, the light hydrocarbons include C1-C4 alkanes, especially methane-ethane.
As an example, the operating temperature of the microchromatography column is below 300 ℃.
As an example, the micro-pillars 400 may include elliptical micro-pillars or circular micro-pillars, and when the micro-pillars 400 employ elliptical micro-pillars, a long axis direction of the elliptical micro-pillars is parallel to an extending direction of the micro-channel 300, and a short axis direction of the elliptical micro-pillars is parallel to a width direction of the micro-channel 300.
In particular, in this embodiment, it is preferable that the microcolumn 400 is an elliptical microcolumn, and the n×m elliptical microcolumn array located in the microchannel 300 can greatly reduce the area of the "quasi-zero flow velocity zone" formed after the microcolumn, so that the FG-HKUST-1 stationary phase 700 coated on the microcolumn 400 can be more uniform, and the flow velocity distribution in the column is uniform.
As an example, the cover plate 500 may include a glass cover plate, a silicon cover plate, or a ceramic cover plate. Among them, it is preferable that the cap plate 500 is made of the same material as the substrate 100 in order to form the FG-HKUST-1 stationary phase 700 uniformly in the closed micro channel 600.
As an example, the adjacent n columns of the micro pillars 400 are equally spaced in the width direction along the micro channel 300 to reduce process complexity; or in the width direction along the micro channel 300, the n columns of micro columns can be arranged to have different intervals according to the requirement, so that the flow velocity distribution in the columns is further uniform, and the problem of uneven flow velocity of carrier gas is relieved.
As an example, the spacing S of adjacent n columns of the micro-pillars 400 is smaller than the spacing S between the micro-pillars 400 and the micro-channel sidewall 110 at the edges, i.e., S > S, in the width direction of the micro-channel 300 to provide a uniform flow rate in the micro-channel 300.
By way of example, the topography of the microchannel 300 includes one of serpentine, polyline, U-shaped, and spiral extensions.
In summary, according to the micro-chromatographic column for separating light hydrocarbons and the preparation method thereof provided by the invention, FG and HKUST-1 are adopted to prepare FG-HKUST-1 stationary phase of the micro-chromatographic column, and FG-HKUST-1 stationary phase is made of nonpolar material, and besides the screening effect on the light hydrocarbons of C1-C4, further, chromatic dispersion exists between the nonpolar FG-HKUST-1 stationary phase and the nonpolar light hydrocarbons, such as nonpolar methane and ethane, so that the nonpolar FG-HKUST-1 stationary phase has stronger retention capacity for the nonpolar light hydrocarbons, and the separation degree of the light hydrocarbons of C1-C4 can be improved, especially for the light hydrocarbons with low separation degree, great concentration difference and relatively close properties, such as methane and ethane, so that the requirements for qualitative and quantitative analysis and detection of the light hydrocarbons can be met.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. A microcohromatography column for light hydrocarbon separation, characterized in that it comprises:
a substrate;
a microchannel located in the substrate, the microchannel having a first port and a second port;
the micro-columns are positioned in the micro-channels, n rows of the micro-columns are arranged at intervals in the width direction of the micro-channels, and m rows of the micro-columns are arranged at intervals in the extending direction of the micro-channels so as to form an n multiplied by m micro-column array;
the cover plate is positioned on the surface of the substrate and covers the micro-channel to form a closed micro-channel;
an FG-HKUST-1 stationary phase, the FG-HKUST-1 stationary phase covering the closed microchannel inner surface, materials forming the FG-HKUST-1 stationary phase comprising FG and HKUST-1, the FG-HKUST-1 stationary phase having a sieving effect, and the FG-HKUST-1 stationary phase being a nonpolar material.
2. The microchromatography column of claim 1 wherein: the light hydrocarbon comprises C1-C4 alkane.
3. The microchromatography column of claim 1 wherein: the operating temperature of the micro-chromatographic column is below 300 ℃.
4. The microchromatography column of claim 1 wherein: the microcolumn comprises an elliptical microcolumn or a circular microcolumn, when the microcolumn is an elliptical microcolumn, the long axis direction of the elliptical microcolumn is parallel to the extending direction of the microchannel, and the short axis direction of the elliptical microcolumn is parallel to the width direction of the microchannel.
5. The microchromatography column of claim 1 wherein: the cover plate comprises a glass cover plate, a silicon cover plate or a ceramic cover plate.
6. The microchromatography column of claim 1 wherein: the micro-channel comprises one of serpentine extension, fold line extension, U-shaped extension and spiral extension.
7. The preparation method of the micro chromatographic column for separating light hydrocarbons is characterized by comprising the following steps of:
providing a substrate, and forming a patterned mask layer on the surface of the substrate;
etching the substrate based on the patterned mask layer to form a micro-channel and micro-columns in the substrate, wherein the micro-channel is provided with a first port and a second port, the micro-columns are positioned in the micro-channel, n columns of the micro-columns are arranged at intervals in the width direction of the micro-channel, and m rows of the micro-columns are arranged at intervals in the extending direction of the micro-channel so as to form an n multiplied by m micro-column array;
providing a cover plate, and bonding the cover plate to the surface of the substrate to cover the micro-channel to form a closed micro-channel;
forming an FG-HKUST-1 stationary phase, the FG-HKUST-1 stationary phase covering the closed microchannel inner surface, the material forming the FG-HKUST-1 stationary phase comprising FG and HKUST-1, the FG-HKUST-1 stationary phase having a sieving effect, and the FG-HKUST-1 stationary phase being a non-polar material.
8. The method of preparing a microcohromatography column according to claim 7, wherein the step of forming the FG-HKUST-1 stationary phase comprises:
mixing FG-HKUST-1 powder with a solvent to prepare FG-HKUST-1 solution;
injecting the FG-HKUST-1 solution into the closed microchannel from the first port and exiting through the second port to coat FG-HKUST-1 material in the closed microchannel;
an aging treatment is performed to convert the FG-HKUST-1 material into an FG-HKUST-1 stationary phase that covers the inner surface of the closed microchannel.
9. The method of preparing a microcohromatography column according to claim 8, wherein: the preparation method of the FG-HKUST-1 powder comprises the following steps:
placing FG powder into DMF solvent, ultrasonic dispersing and standing, and collecting supernatant;
in Cu (NO) 3 ) 2 ·3H 2 O powder and H 3 Adding DMSO solvent into BTC powder, and performing ultrasonic dispersion and dissolution to obtain a mixed solution;
on CH 3 Adding the supernatant and the mixed solution into the OH solution, stirring and centrifugally separating to obtain a lower layer solid;
by CH 3 Washing with OH solution, and drying to obtain FG-HKUST-1 powder.
10. The method of preparing a microcohromatography column according to claim 7, wherein: the method further comprises the step of dicing after bonding the cover plate and before forming the FG-HKUST-1 stationary phase.
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