CN110420567B - Preparation method of graphene hydrophobic membrane and application method of membrane distillation - Google Patents
Preparation method of graphene hydrophobic membrane and application method of membrane distillation Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
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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
- B01D67/0039—Inorganic membrane manufacture
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2323/04—Hydrophobization
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a preparation method of a graphene hydrophobic membrane, which comprises the following steps: (1) processing the graphene oxide to prepare reduced graphene oxide; (2) preparing graphene oxide or reduced graphene oxide prepared in the step (1) into a graphene hydrophobic membrane; (3) and (3) carrying out hydrophobic treatment on the graphene hydrophobic membrane. The invention also provides a membrane distillation application method based on the graphene hydrophobic membrane, which comprises the following steps: assembling the prepared graphene hydrophobic membrane into a separation membrane component, then contacting liquid containing different isotopes with the separation membrane component, and separating multiple media by utilizing a membrane distillation mode. The invention prepares a novel graphene hydrophobic membrane by a simple process, and then combines the characteristics of membrane distillation to realize H2O/D2O、H2O/T2O、H2 16O/H2 18O and the like. The invention has high separation efficiency, does not need to heat liquid into steam, has low energy consumption, and is very easy to be applied in scale based on the process route of membrane distillation.
Description
Technical Field
The invention relates to the technical field of hydrogen isotope separation, in particular to a preparation method of a graphene hydrophobic membrane and an application method of membrane distillation.
Background
The treatment of liquids containing radioactive elements involves a number of fields, such as the treatment of tritium (T) -containing liquids in the nuclear power field (X.X. Mei, L.P.Xiong et al, Analytical chemistry 2010,33, 201-2 18O preparation (J.K.Choi, D.S.Chang et al, Ind.Eng.chem.Res.2009,48, 5431-5438). In the nuclear power field, tritium from fission reactors may come from reactors and after-treatment plants, including heavy water as neutron moderator in heavy water reactors(D2O) will undergo neutron capture to produce tritium, which is present in the moderator as HTO. In fusion reactors, tritiated water (T)2O) is mainly derived from an atmospheric detritiation system, which oxidizes tritium-containing gases leaked by the tritium-involving system of the entire Fusion stack, and adsorbs them with a sorbent, and then treated by a water detritiation system (y.iwai, y.misaki et al, Fusion Science and Technology,2002,41, 1126-. In these tritium-containing liquids, not only the amount of tritium-containing liquid is large, but also the concentration of tritium-containing liquid is low. The tritium-containing liquid component comprises H2O, HTO and T2The processes for tritium removal from heavy water which have been reported for large-scale use abroad are VPCE + CD (gas phase catalytic exchange + cryogenic rectification), LPCE (liquid phase catalytic exchange), all of which are relatively complex and have many steps (J.P. Butler, Separation Science and Technology,1980, 15371-396). No matter based on the recycling of tritium in tritium-containing wastewater, or the safe and environment-friendly consideration of reducing the content of radioactive tritium in water, the development of tritium-containing wastewater treatment technology is an essential process in nuclear energy industry, especially the treatment of low tritium water, and relates to light water (H)2O), HTO and tritiated water (T)2O), is still a difficult point to solve (s.g. luo, radioprotection, 1993,13, 158-. Since tritium is radioactive, heavy water (D) which is free from radioactivity and has similar chemical properties is generally used in view of safety and simplification problems2O) instead of tritiated water (T)2O), study on Low tritium liquid handling frequently H2O/D2Isolation of O was the subject of investigation.
In view of the problem of tritium-containing liquid treatment, based on the latest research that graphene oxide films can selectively permeate water vapor, (r.r.nair, h.a.wu et al, Science,2012,335, 442-2O/D2O,H2O/T2Work of O (GJ Sevigny, Separation of textured water using graphene oxide membrane,2015), experiments show that graphene oxide prepared by Hummers method is used for graphene oxide membrane separation H through vacuum filtration2O/D2O, when the graphene particle size is 100nm, H2O/D2The separation effect of O has no direct correlation with the film thickness, and H is generated when the particle size of the graphene is 500nm-5 μm or 5-15 μm2O/D2The separation effect of O has a certain correlation with the film thickness, and the thicker the film, the better the separation effect, but the thicker the film, the lower the transmittance.
Separation by2O/D2O,H2O/T2The O test method has a static diffusion experiment, and is similar to the graphene oxide membrane water permeation experiment, namely under the condition of controlling humidity, the permeation performance of the graphene membrane is preliminarily tested by measuring the weight loss of water permeating the graphene oxide membrane within a certain time; permeation Rate test, permeation H2O or D2O gas was analyzed by Residual Gas Analyzer (RGA) mass spectrometry; and a distilled gas permeation experiment, wherein liquid is vaporized by heating, passes through the graphene oxide under the action of pressure difference and is condensed. Best H2O/D2O,H2O/T2The O separation efficiencies are 1.25 and 1.6, respectively, on the basis of which, according to calculations, particularly large membranes or separation stages are necessary to make it possible to carry out meaningful separation work.
In addition, the membrane distillation (membrane distillation) method is considered to be a promising water treatment method, and first, since membrane distillation is performed by a partial pressure difference between vapor located at one side of a separation membrane and vapor located at the other side thereof, membrane distillation can be performed at a lower pressure than ultrafiltration or reverse osmosis; secondly, additional pressure is not required for membrane distillation; again, membrane distillation can be used to remove non-volatile ionic materials by separation; fourth, membrane distillation can collect water at a predetermined rate without being affected by the concentration of contaminants contained in the feed water.
It can be said that membrane distillation combines conventional distillation with other membrane separation processes, such as Flash evaporation (Flash) and reverse osmosis (reverse osmosis). Membrane distillation requires membranes of special properties to allow the gas to pass from the hot end to the cold end. The membrane must be large and the holes must be large to allow gas to pass through but prevent liquid from passing through; at the same time, the film must also be as thin as possible. Membrane distillation processes use membrane materials that are generally hydrophobic, and during membrane distillation, the hydrophobic membrane selectively allows vapor to pass from the hot fluid side to the cold fluid side, while the membrane restricts liquid flow. The driving force for the vapor to pass through the membrane is the difference in vapor pressure and temperature across the membrane.
The process route based on membrane distillation itself is simple, scalable, and has been adopted as a leading-edge method for Desalination of sea water (D.Amaya-V.ias, E.Nebot et al, Desalination,2018,429, 44-51), and treatment of radioactive-containing waste streams (X.Wen, F.Li et al, Nuclear Technology,2016,194, 379-386), and in order to explore the treatment of tritium-containing liquids, Polish Nuclear scientists have developed membrane distillation for the separation of H2O/HDO and H2 16O/H2 18O work (g.zakrzewska-Trznadel, a.g. chimielewski et al, j.mem.sci.1996,113, 337-342) used two commercial polytetrafluoroethylene membranes with pore sizes of 0.2 μm and 0.84 μm, and thicknesses of 175 μm and 60 μm, respectively, depending on the membrane material used, the mass transfer mechanism for membrane distillation could be either diffusion (dispersive) or convective (convective) mode, especially the pore size of the membrane material has a significant effect on the mass transfer mechanism, knuddsiffusion when the pore size is small, i.e. smaller than the free path of water molecules, and the mass transfer mechanism in the absence of air is mainly that of the poiseule flow model (viscofluxes) when the pore size is larger than the free path of water molecules. Combining theoretical calculation and experimental results, separating H by membrane distillation2The mechanism of O/HDO is the combined action of the atmospheric pressure isotope effect (VPIE) and the diffusion isotope effect (VPIE) on H2For O/HDO separation, the gas pressure isotope effect plays a major role for H2 16O/H2 18For O separation, the diffusion isotope effect plays a major role. Obtained by multistage series connection of the direct contact membrane distillation methodH2O/HDO and H2 16O/H2 18The Separation efficiency of O is 1.04 and 1.06, respectively, and the Separation efficiency is still very low (A.G. Chmielewski, G.Zakrzewska-Trznadel et al, Separation Science and Technology,1997,32, 527-.
On the basis of these works, Korea and Iran scientists faced the medical industry to H2 18O, separation of H by membrane distillation2 16O/H2 18O, found that PVDF membranes prepared by electrospinning have higher membrane separation efficiency than commercial PTFE (R. Moradi, J. Karimi-Sabet et al, Chemical Engineering and Processing: Process integration, 2016,100, 26-36), and compared different types of membrane distillation separation processes (E. Karbasi, J. Karimi-Sabet et al, Chemical Engineering Journal,2017,322, 667-.
In summary, it can be seen that treatment of tritium-containing liquids, such as H, can be achieved using graphene films or membrane distillation2O/D2O、H2O/T2O, even H2 16O/H2 18O。
However, the existing methods for treating tritium-containing liquid have high energy consumption and cannot be applied in large scale, or the separation efficiency of the membrane is low, so that the requirements of practical application cannot be well met. To separate H2O/D2O for example, heating a liquid to a vapor based on a graphene membrane through gas phase separation, although H2O/D2O、H2O/T2The O separation efficiency is 1.25 and 1.6 respectively, and certain separation efficiency exists, but because liquid needs to be heated into steam, the energy consumption is very high, and no large-scale application example exists at present; the hydrophobic separation membrane is separated by a membrane distillation method, the membrane separation mechanism is basically clear, the membrane separation membrane can be used in a multi-stage combination mode, the process energy consumption is low, the large-scale application is easy, but H is2The O/HDO ratio was only 1.04, and the separation efficiency was not high.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a graphene hydrophobic membraneAnd the application method of membrane distillation, aiming at increasing H2O/D2O、H2O/T2O or even H2 16O/H2 18And the separation efficiency of various media such as O and the like is improved, the energy consumption is reduced, and the purpose of large-scale application is realized.
In order to achieve the above purpose, the present invention adopts the following two technical solutions based on a general inventive concept:
scheme one
A preparation method of a graphene hydrophobic membrane comprises the following steps:
(1) adding graphene oxide powder into a solvent to prepare a suspension dispersion liquid;
(2) and removing the solvent in the suspension dispersion solution, and then performing hydrophobic treatment to obtain the graphene hydrophobic membrane.
Preferably, the solvent in step (2) is water.
Scheme two
A preparation method of a graphene hydrophobic membrane comprises the following steps:
(1) processing graphene oxide to obtain reduced graphene oxide;
(2) adding reduced graphene oxide powder into a solvent to prepare a suspension dispersion liquid;
(3) and removing the solvent in the suspension dispersion solution, and then performing hydrophobic treatment to obtain the graphene hydrophobic membrane.
Preferably, the solvent in step (3) is a polar solvent.
In the two schemes, the suspension dispersion liquid is preferably prepared by adopting an ultrasonic mode.
And the mode adopted for removing the solvent is preferably as follows: and (3) inputting the suspension dispersion liquid of the graphene into a filtering container containing a supporting carrier, then filtering out the solvent, and preferably removing the solvent by adopting a suction filtration mode.
In addition, the hydrophobic treatment of the graphene hydrophobic membrane is realized by adopting a liquid treatment method or a gas treatment method. The method of liquid treatment is as follows:
a. preparing a hydrophobic treatment solution;
b. immersing the graphene hydrophobic membrane into hydrophobic treatment liquid, taking out after treating for a certain time, and airing at room temperature;
c. and heating the graphene hydrophobic membrane subjected to hydrophobic treatment for a certain time, taking out, and finally cooling to room temperature.
The arrangement mode of the graphene in the graphene hydrophobic membrane prepared by the invention is any one of horizontal arrangement, inclined arrangement and vertical arrangement.
Based on the two schemes for preparing the graphene hydrophobic membrane, the invention also provides an application method of membrane distillation associated with the graphene hydrophobic membrane, which comprises the following steps:
(1) assembling the graphene hydrophobic membrane obtained by the scheme into a separation membrane component;
(2) the liquid containing different isotopes contacts with a separation membrane component, and the separation of various media in the liquid is realized by utilizing a membrane distillation mode.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes graphene oxide as a base, prepares a novel graphene hydrophobic membrane by a simple process, and then combines the characteristics of membrane distillation to realize H2O/D2O、H2O/T2O、H2 16O/H2 18O and the like. The invention has high separation efficiency, does not need to heat liquid into steam, has low energy consumption, and is very easy to be applied in scale based on the process route of membrane distillation. It should be noted that the invention breaks through the limitation of the prior art by ingenious design, provides a technical means with high feasibility for the treatment of the liquid containing different isotopes, and plays a very important role in the fields of tritium-containing liquid treatment, medical use and the like.
Drawings
Fig. 1 is a flow chart of the preparation of the graphene hydrophobic membrane according to the present invention.
Fig. 2 is a schematic structural view of a separation membrane module used in an example of the present invention.
Fig. 3 is a graph showing the difference of deuterium abundance between raw water and filtered water when different graphenes are loaded on PTFE membranes with 0.25 μm pore size according to the example of the present invention.
Fig. 4 shows the difference of deuterium abundance between raw water and filtered water when different graphenes are loaded on PTFE membranes with 1 μm pore size in the example of the present invention.
Detailed Description
The present invention will be further described with reference to the following description and examples, which include but are not limited to the following examples.
The invention provides a novel preparation method of a graphene hydrophobic membrane, and the obtained graphene hydrophobic membrane can be well applied to separation of multiple media (such as H) in liquids containing different isotopes by combining a membrane distillation method2O/D2O、H2O/T2O、 H2 16O/H2 18O, etc.).
Example 1
The process for preparing the graphene hydrophobic membrane in this example is as follows:
(1) adding graphene oxide powder into a solvent to prepare a suspension dispersion liquid; this example uses ultrasound to prepare the suspension dispersion, and also can use physical shaking, vibration or stirring to prepare the suspension dispersion. The graphene may be single-layer, double-layer, or multi-layer graphene, and the state in which the graphene exists may be disordered graphene powder or a liquid suspension.
(2) The solvent (e.g., water) in the suspension dispersion solution is removed, and then hydrophobic treatment is performed, so that the graphene hydrophobic membrane is obtained. For example, a suspension dispersion of graphene is fed into a filtration vessel containing a support carrier, and then the solvent is filtered off (suction filtered). In addition, the arrangement mode of the graphene in the graphene hydrophobic film is not considered, and the arrangement mode of the graphene can be disordered, such as horizontal arrangement, inclined arrangement or vertical arrangement.
The hydrophobic treatment method for the graphene hydrophobic membrane may be a liquid treatment method or a gas treatment method, for example, when the liquid treatment method is adopted, a hydrophobic treatment solution may be prepared first, and this embodiment provides a preparation method of the hydrophobic treatment solution, that is: is prepared by mixing ethanol, 1H,2H, 2H-perfluorooctyltriethoxysilane, 0.1MHCl and water according to the weight ratio of 88: 0.5: 1.5: 10.
After the hydrophobic treatment liquid is prepared, the graphene hydrophobic membrane is immersed in the hydrophobic treatment liquid, taken out after a certain time (for example, 1 hour), dried at room temperature, heated for a certain time (for example, heated for 2 hours at 120 ℃) and then cooled to room temperature, and thus the hydrophobic treatment of the graphene hydrophobic membrane can be completed.
Example 2
The process for preparing the graphene hydrophobic film in this embodiment is different from that in embodiment 1 in that, in this embodiment, first, graphene oxide is treated to obtain reduced graphene oxide (which may be treated by a thermal treatment or a chemical reduction method, for example, graphene oxide with a sheet diameter of more than 5 μm and 1-6 layers is treated for 3 hours at 750 ℃ in an inert atmosphere to obtain reduced graphene oxide), and then, the reduced graphene oxide is prepared into the graphene hydrophobic film in the same manner as in embodiment 1.
Example 3
In this embodiment, based on the graphene hydrophobic films prepared in the above embodiments 1 and 2, the graphene hydrophobic films are combined with a membrane distillation method to realize H2O/D2O, even H2O/T2O、H2 16O/H2 18And (4) separating O. The method specifically comprises the following steps: the graphene hydrophobic membrane is assembled into a separation membrane assembly, and then the liquid to be treated is contacted with the graphene hydrophobic membrane assembly, so that the separation of various media in the liquid is realized. The structure of the separation membrane module is shown in fig. 2.
A blank test based on a PTFE membrane with a pore size of 0.25 μm showed almost right D2O has no enrichment effect, but the supported graphene films prepared by using different graphene materials show that the D content of product water is related to different types of graphene materials in the experimental time, which shows that the graphene films prepared by different treatment methods are used for H2O/D2O has different separation and enrichment effects, as shown in FIG. 3.
Based on a PTFE membrane with a pore diameter of 1 mu m, the D content of the product water is displayed by using supporting graphene membranes prepared from different graphene materialsThe amount is related to different types of graphene materials in the experimental time, and shows that the graphene films of different treatment methods are used for H2O/D2O has different separation and enrichment effects, as shown in FIG. 4.
The invention effectively combines the respective advantages of the graphene hydrophobic membrane and the membrane distillation, and simultaneously avoids the respective disadvantages of the graphene hydrophobic membrane and the membrane distillation, so that the graphene hydrophobic membrane and the membrane distillation can be better used for realizing H2O/D2O、H2O/T2O、H2 16O/H2 18O and the like. Compared with the prior art, the invention realizes 1+1>2, the technical progress is very obvious, the effect is unpredictable, and the method has prominent substantive features and remarkable progress.
The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.
Claims (7)
1. An application method for preparing a graphene hydrophobic membrane for membrane distillation is characterized by comprising the following steps:
firstly, preparing a graphene hydrophobic membrane by adopting the following steps:
(1) adding graphene oxide powder into a solvent to prepare a suspension dispersion liquid;
(2) removing the solvent in the suspension dispersion solution, wherein the solvent removal mode is as follows: inputting the suspension dispersion liquid of the graphene into a filtering container containing a supporting carrier, then filtering out a solvent, wherein the supporting carrier is a PTFE membrane,
then carrying out hydrophobic treatment to obtain a graphene hydrophobic membrane of the PTFE membrane loaded with graphene; the arrangement mode of the graphene in the graphene hydrophobic membrane is horizontal arrangement, inclined arrangement or vertical arrangement;
assembling the obtained graphene hydrophobic membrane into a separation membrane component;
finally, the liquid containing different isotopes contacts with a separation membrane component, and the separation of various media in the liquid is realized by utilizing a membrane distillation mode.
2. The application method of preparing the graphene hydrophobic membrane for membrane distillation as claimed in claim 1, wherein the solvent in step (2) is water.
3. An application method for preparing a graphene hydrophobic membrane for membrane distillation is characterized by comprising the following steps:
firstly, preparing a graphene hydrophobic membrane by adopting the following steps:
(1) processing graphene oxide to obtain reduced graphene oxide;
(2) adding reduced graphene oxide powder into a solvent to prepare a suspension dispersion liquid;
(3) removing the solvent in the suspension dispersion solution, wherein the solvent removal mode is as follows: inputting the suspension dispersion liquid of the graphene into a filtering container containing a supporting carrier, then filtering out a solvent, wherein the supporting carrier is a PTFE membrane,
then carrying out hydrophobic treatment to obtain a graphene hydrophobic membrane of the PTFE membrane loaded with graphene; the arrangement mode of the graphene in the graphene hydrophobic membrane is horizontal arrangement, inclined arrangement or vertical arrangement;
assembling the obtained graphene hydrophobic membrane into a separation membrane component;
finally, the liquid containing different isotopes contacts with a separation membrane component, and the separation of various media in the liquid is realized by utilizing a membrane distillation mode.
4. The application method of preparing the graphene hydrophobic membrane for membrane distillation as claimed in claim 3, wherein the solvent in step (3) is a polar solvent.
5. The application method of preparing the graphene hydrophobic membrane for membrane distillation as claimed in claim 1 or 3, wherein the suspension dispersion liquid is prepared by an ultrasonic method.
6. The application method of preparing the graphene hydrophobic membrane for membrane distillation as claimed in claim 1 or 3, wherein the solvent is removed by suction filtration.
7. The application method of preparing the graphene hydrophobic membrane for membrane distillation as claimed in claim 1 or 3, wherein the hydrophobic treatment of the graphene hydrophobic membrane is realized by a liquid treatment method or a gas treatment method.
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