CN107441892B - Application of two-dimensional MXene membrane in gas separation - Google Patents
Application of two-dimensional MXene membrane in gas separation Download PDFInfo
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- CN107441892B CN107441892B CN201710614632.0A CN201710614632A CN107441892B CN 107441892 B CN107441892 B CN 107441892B CN 201710614632 A CN201710614632 A CN 201710614632A CN 107441892 B CN107441892 B CN 107441892B
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- 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
- B01D53/22—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 diffusion
- B01D53/228—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 diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
Abstract
The invention discloses an application of a two-dimensional MXene membrane in gas separation. The application comprises the following steps: (1) putting the two-dimensional MXene membrane into a gas separation device, and then introducing mixed gas to be separated into the gas separation device at a feed side; (2) introducing a purge gas at the purge side; (3) the purge gas was passed through a gas chromatograph for detection. The MXene film of the invention has ultra-high H2Ultra high transmission H2/CO2，H2/N2,H2/CH4，H2/C3H6And H2/C3H8The separation selectivity and the excellent mechanical property, and the preparation method of the two-dimensional MXene membrane is simple and easy to operate, low in energy consumption, low in cost, high in repeatability and suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the field of nano-film and membrane method gas separation, and particularly relates to an application of a two-dimensional MXene membrane in gas separation.
Background
Since the industrial revolution, separation has been a very important part of industrial production, especially gas separation. Conventional gas separation processes include distillation separation and pressure swing adsorption. However, these separation processes have high energy consumption, complicated operation, large equipment floor space, low separation efficiency, and the like. To address these problems, researchers are actively developing efficient and sustainable separation technologies. Among them, the membrane separation technology represents a development direction of a novel solution by its high efficiency and energy saving characteristics.
The types of membrane separation materials are wide. Organic polymer films were first developed, but have problems of poor thermal stability and low permeation. The subsequent ceramic membrane solves the problem of thermal stability of the organic polymer membrane, but has high cost, complex preparation process and difficult large-scale application. Therefore, an ideal membrane should have both the ease of preparation of an organic membrane and the stability of a ceramic membrane.
In recent years, two-dimensional nanomembranes represented by graphene oxide have been successfully produced and applied to the field of separation. The two-dimensional nano-film has the characteristics of good thermal stability, strong chemical stability, excellent mechanical property, simple preparation, high separation performance and the like. Recently, MXene, a two-dimensional nanomaterial, has been successfully developed and has attracted a wide range of attention from scientists. Compared with common graphene oxide, MXene has the excellent characteristics of simpler preparation process, better hydrophilicity, stronger conductivity and the like. It has been confirmed that MXene films of the same thickness separate better than graphene oxide films. Therefore, the two-dimensional MXene membrane is expected to show wider application prospect in the separation field.
Here we developed a low cost, high permeability and high selectivity MXene membrane for gas separation.
Disclosure of Invention
In order to improve the prior art and to achieve a major breakthrough in the field of gas separation, it is an object of the present invention to provide a use of a two-dimensional MXene membrane in gas separation. The two-dimensional MXene membrane can be used for industrial hydrogen purification and carbon dioxide capture.
The purpose of the invention is realized by the following technical scheme.
The application of a two-dimensional MXene membrane in gas separation comprises the following steps:
(1) putting the two-dimensional MXene membrane into a gas separation device, and then introducing mixed gas with different kinetic diameters to be separated into the gas separation device at the feed side;
(2) introducing a purge gas at the purge side;
(3) and (3) introducing the purge gas in the step (2) into a gas chromatograph for detection, so as to obtain the permeation amount and selectivity of different gases.
Preferably, the mixed gas is helium (He, 0.26 nm) or hydrogen (H)20.29 nm), twoCarbon Oxide (CO)20.33 nm), oxygen (O)20.346 nm), nitrogen (N)20.364), methane (CH)40.4 nm), ethylene (C)2H40.39 nm), propane (C)2H60.42 nm), propylene (C)3H60.4 nm) and propane (C)3H80.43 nm), e.g. H2/CO2， H2/N2,H2/CH4，H2/C2H4，H2/C2H6，H2/C3H6，H2/C3H8，C2H4/C2H6And C3H6/C3H8One or more combinations thereof.
Preferably, the flow rate of the mixed gas is 10-1000 ml/min.
Preferably, the purge gas is one or more of nitrogen and argon.
Preferably, the flow rate of the purge gas is 10-1000 ml/min.
Preferably, the gas chromatography is agilent 7890A gas chromatography.
The preparation method of the two-dimensional MXene film comprises the following steps:
(1) mixing lithium salt with acid solution to obtain mixed solution; adding the three-dimensional layered MAX phase powder into the mixed solution, uniformly stirring, centrifugally washing, and drying to obtain MXene powder;
(2) mixing MXene powder with a solvent, performing ultrasonic treatment and centrifugation to obtain supernatant, namely a solution containing two-dimensional MXene nanosheets;
(3) and (3) accumulating the solution containing the two-dimensional MXene nanosheets obtained in the step (2) on a polyether sulfone filter membrane (PES) substrate through a nano-assembly technology, and drying to obtain the two-dimensional MXene membrane.
Preferably, the lithium salt in the step (1) is more than one of lithium chloride, lithium bromide, lithium sulfate and lithium nitrate; the acid solution is more than one of phosphoric acid, sulfuric acid and nitric acid; the above-mentionedThe MAX phase powder of (B) is Ti2AlC、V2AlC、Ti3SiC2、Ti3AlC2、Ti4AlN3And Nb4AlC3More than one of them.
Preferably, the mass-to-volume ratio of the lithium salt to the acid solution in the step (1) is 1 g: (100-200) mL; the volume concentration of the acid solution is 10-40%.
Preferably, the mass of the MAX phase powder in the step (1) is 100 g-200 g
Preferably, the time for stirring uniformly in the step (1) is 24-48 hours.
Preferably, the rotating speed of the stirring in the step (1) is 50-600 rpm; the centrifugal rotating speed is 1000-8000 rpm; the centrifugation time is 5-100 min.
Preferably, the washing in the step (1) is washing with deionized water for 2-10 times.
Preferably, the drying conditions in step (1) are one or more of drying in an air drying oven, freeze drying and vacuum drying; the drying temperature is 30-200 ℃; the drying time is 4-48 hours.
Preferably, the solvent in the step (2) is more than one of ethanol, dimethyl sulfoxide, water, N-methyl pyrrolidone, polycarbonate and dimethylformamide; the mass volume ratio of MXene powder to solvent is 1 g: (500-2000) ml.
Preferably, the ultrasonic time in the step (2) is 1-8 hours.
Preferably, the centrifugal rotating speed in the step (2) is 500-5000 rpm; the centrifugation time is 1-3 hours.
Preferably, the concentration of the solution containing the two-dimensional MXene nanosheets in the step (3) is 0.05-5 mg/ml.
Preferably, the nano self-assembly technology in the step (3) is one or more of a spraying method, a spin coating method, a natural drying method and a vacuum filtration method.
Preferably, the pore diameter of the polyethersulfone filter membrane (PES) substrate in the step (3) is 0.5 μm, and the diameter is 10-500 mm.
Preferably, the drying conditions in step (3) are one or more of drying in an air drying oven, freeze drying and vacuum drying; the drying temperature is 100-300 ℃; the drying time is 10-48 hours.
A two-dimensional MXene film produced by the above-described process can be easily peeled off from a substrate as a free-standing unsupported film with excellent flexibility and mechanical properties.
According to the invention, the two-dimensional MXene membrane prepared by self-assembling the two-dimensional MXene nanosheets is applied to selective gas separation for the first time, and has high H content2Penetration, high H2/CO2，H2/N2, H2/CH4，H2/C2H4，H2/C2H6，H2/C3H6And H2/C3H8And the prepared highly-ordered MXene gas separation membrane has great application value.
Compared with the prior art, the invention has the following advantages:
(1) the two-dimensional MXene membrane of the invention is used for separating H-containing2Has an ultra-high H content in the mixed gas of (1)2The permeation quantity and the high gas selectivity have good application prospect in the gas separation membrane.
(2) The two-dimensional MXene film is a self-supporting film, does not need any substrate, is simple in preparation process and low in energy consumption, and can greatly save cost in practical application.
(3) The two-dimensional MXene film has good repeatability and is suitable for large-scale industrial production.
Drawings
Fig. 1 is a graph of transmission analysis of the two-dimensional MXene membrane prepared in example 1 applied to gas separation.
Fig. 2 is a diagram showing the selective analysis of the two-dimensional MXene membrane prepared in example 1 applied to gas separation.
Detailed Description
Specific embodiments of the present invention will be further described below with reference to examples and the accompanying drawings, but embodiments of the present invention are not limited thereto.
Example 1
A preparation method of a two-dimensional MXene film comprises the following steps:
(1) 1g of lithium fluoride is first mixed with 100ml of hydrochloric acid solution (volume concentration: 10%), and 1g of three-dimensionally layered Ti is then added3AlC2Adding the powder into the solution, stirring for 2h, centrifuging at 1000rpm, washing, and drying to obtain Ti3C2Powder;
(2) mixing 1g of Ti3C2Mixing the powder with 500ml of ethanol, performing ultrasonic treatment for 1h, and then centrifuging at the rotating speed of 500rpm for 1h to obtain supernatant, wherein the obtained supernatant is a solution containing two-dimensional MXene nanosheets, and the concentration is 5 mg/ml;
(3) and (3) accumulating the solution of the two-dimensional MXene nanosheets on a polyether sulfone filter membrane (PES) substrate with the aperture of 0.5 mu m and the diameter of 10mm by a spraying method, and drying in a forced air drying oven at 100 ℃ for 10 hours to obtain the two-dimensional MXene membrane.
Application of the two-dimensional MXene membrane of this example in gas separation:
placing the two-dimensional MXene membrane into a gas separation device, and respectively introducing H into the gas separation device at the feed side2/CO2、H2/N2、H2/CH4、H2/C3H6、H2/C3H8The flow rate of the mixed gas (10 ml/min) is 1:1, and N is introduced during blowing2(the flow rate is 10 ml/min) and then the mixture is introduced into a gas chromatograph for detection. The permeation amount of various gases is measured through experiments as follows: pH2=1201 GPU， PCO2=5 GPU，PN2=9 GPU, PCH4=1.5 GPU， PC3H6=0.95 GPU and PC3H8=0.59 GPU（1GPU= 1×10−6cm3/cm2Sec cmHg at STP). The results are shown in FIG. 2. Separation selectivity is respectively H2/CO2：166.6， H2/N2：77.6,H2/CH4：324，H2/C3H6：781，H2/C3H8: the results are shown in FIG. 2 at 1101.
Example 2
A preparation method of a two-dimensional MXene film comprises the following steps:
(1) 1g of lithium bromide was mixed with 200ml of a hydrochloric acid solution (volume concentration: 40%), and 100g of three-dimensionally layered Ti was added3AlC2Adding the powder into the solution, stirring for 48h, centrifuging at 8000rpm, washing, and drying to obtain Ti3C2Powder;
(2) mixing 1g of Ti3C2Powder and 2000 ml H2O, mixing, performing ultrasonic treatment for 8 hours, and then centrifuging for 3 hours at the rotating speed of 5000rpm, wherein the obtained supernatant is a solution containing two-dimensional MXene nanosheets, and the concentration is 2.5 mg/ml;
(3) and (3) accumulating the solution of the two-dimensional MXene nanosheets on a polyether sulfone filter membrane (PES) substrate with the aperture of 0.5 mu m and the diameter of 500mm by a natural drying method, and drying for 48 hours in a vacuum drying oven at 300 ℃ to obtain the two-dimensional MXene membrane.
Application of the two-dimensional MXene membrane of this example in gas separation:
placing the two-dimensional MXene membrane into a gas separation device, and introducing H on the feed side2/ CH4The volume ratio of the mixed gas (flow rate is 1000ml/min) is 1:1, and N is introduced by blowing2(flow rate 1000ml/min) was passed through a gas chromatograph for detection. The permeation quantities of hydrogen and methane measured by the experiment are respectively as follows: pH2=1015 GPU、PCH4=1.7 GPU。H2/ CH4The separation selectivity of (a) is 777.
Example 3
A preparation method of a two-dimensional MXene film comprises the following steps:
(1) 1g of lithium bromide was mixed with 150ml of a nitric acid solution (35% by volume), and 20g of three-dimensionally layered Ti was added3AlC2Adding the powder into the solution, stirring for 14h, centrifuging at 2000rpm, washing, and drying to obtain Ti3C2Powder;
(2) mixing 5g of Ti3C2Powder and 500mixing ml of dimethyl sulfoxide, performing ultrasonic treatment for 2 hours, and then centrifuging at the rotating speed of 5000rpm for 1 hour to obtain supernatant, wherein the obtained supernatant is a solution containing two-dimensional MXene nanosheets, and the concentration of the supernatant is 0.25 mg/ml;
(3) and (3) accumulating the solution of the two-dimensional MXene nanosheets on a polyether sulfone filter membrane (PES) substrate with the aperture of 0.5 mu m and the diameter of 100mm by a vacuum filtration method, and drying in a vacuum drying oven at 80 ℃ for 12h to obtain the two-dimensional MXene membrane.
Application of the two-dimensional MXene membrane of this example in gas separation:
placing the two-dimensional MXene membrane into a gas separation device, and introducing H on the feed side2/ C3H8The mixed gas (flow rate 500 ml/min) was measured at a volume ratio of 1:1, and argon gas (flow rate 500 ml/min) was introduced into the gas chromatograph for detection. The permeation quantities of hydrogen and methane measured by the experiment are respectively as follows: pH2=1218 GPU、PC3H8=0.89 GPU。H2/C3H8The separation selectivity of (3) is 1274.3.
The above embodiments are preferred embodiments of the present invention, but the technical implementation of the present invention is not limited to the above embodiments, and any other simplification, change, substitution, modification and combination made without departing from the principle and spirit of the present invention should be regarded as equivalent replacement ways, and all such changes and modifications are included in the scope of the present invention.
Claims (4)
1. Use of a two-dimensional MXene membrane in gas separation comprising the steps of:
(1) putting the two-dimensional MXene membrane into a gas separation device, and then introducing mixed gas to be separated into the gas separation device at a feed side;
(2) introducing a purge gas at the purge side;
(3) introducing the purge gas in the step (2) into a gas chromatograph for detection;
the mixed gas is H2/CO2， H2/N2, H2/CH4，H2/C2H4，H2/C2H6，H2/C3H6And H2/C3H8One or more combinations thereof.
2. Use according to claim 1, characterized in that: the flow rate of the mixed gas is 10-1000 mL/min.
3. Use according to claim 1, characterized in that: the purge gas is more than one of nitrogen and argon.
4. Use according to claim 1, characterized in that: the flow rate of the purge gas is 10-1000 mL/min.
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| CN108183205A (en) * | 2017-12-13 | 2018-06-19 | 中航锂电（江苏）有限公司 | A kind of sodium-ion battery flexible self-supporting electrode material and its application and preparation method |
| CN109397825B (en) * | 2018-12-03 | 2020-07-03 | 武汉市银莱制衣有限公司 | MXene-based composite material with mine dust and toxic gas alarming and filtering functions and preparation method thereof |
| CN109553103B (en) * | 2018-12-14 | 2021-12-21 | 华南理工大学 | Two-dimensional self-crosslinking MXene film and preparation method thereof |
| CN109569319B (en) * | 2018-12-14 | 2021-12-21 | 华南理工大学 | Application of two-dimensional self-crosslinking MXene membrane in ion separation |
| CN112808030B (en) * | 2020-12-23 | 2022-03-29 | 华南理工大学 | Method for electrochemically preparing self-supporting MXene-ZIF-8 composite membrane |
| CN113058446A (en) * | 2021-03-24 | 2021-07-02 | 昆明理工大学 | Preparation of black phosphorus alkene membrane and application of black phosphorus alkene membrane in gas separation |
| CN113083042B (en) * | 2021-04-12 | 2021-12-21 | 大连理工大学 | Mixed matrix membrane based on MXene/ZIF-8 composite material and preparation method thereof |
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| CN106178979A (en) * | 2016-08-31 | 2016-12-07 | 华南理工大学 | High-performance two-dimensional stratiform Ti3c2mXene film and preparation method thereof and the application in water process |
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