CN108295668B - Graphene composite alumina ceramic nano-filtration membrane, filter, preparation method and application thereof - Google Patents
Graphene composite alumina ceramic nano-filtration membrane, filter, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a graphene composite alumina ceramic nano-filtration membrane, a filter, a preparation method and application thereof, wherein the nano-composite filtration membrane comprises an alumina ceramic membrane and a graphene layer positioned on the surface of at least one side of the alumina ceramic membrane; the aperture of the nano composite filtering membrane is about 1-2 nm. The nano composite filtering membrane provided by the invention has the advantages of good hydrophobicity, large flux, high interception rate, no blockage of the aperture of the membrane, effective interception of water molecules, pollution resistance and easy cleaning. The filter prepared by the filter membrane is particularly suitable for separating water from ethanol; in addition, the preparation method of the nano composite filtering membrane provided by the invention is simple to operate, convenient and practical.
Description
Technical Field
The invention belongs to the technical field of inorganic nano composite materials, and particularly relates to a graphene composite alumina ceramic nano filtering membrane, a graphene composite alumina ceramic nano filtering filter, a preparation method of the graphene composite alumina ceramic nano filtering membrane and the graphene composite alumina ceramic nano filtering filter, and application of the graphene composite alumina ceramic nano filtering membrane and the graphene composite alumina ceramic nano filtering filter.
Background
Since ethanol and water form an azeotrope (the azeotropic liquid composition is 0.894 mole fraction containing ethanol at 101.323kPa, and the constant boiling point temperature is 78.15 ℃), anhydrous ethanol cannot be obtained by a conventional rectification method. Currently for ethanol and water separation, the major industrial technologies include distillation, membrane separation (including pervaporation membrane separation PV and vapor permeation membrane separation VP), and adsorption. Wherein the distillation comprises extractive distillation, rectification by adding salt, azeotropic distillation and the like. Compared with a distillation method, the membrane separation method has the advantages of energy conservation, environmental protection, simple operation and the like, and is more effective for separating the azeotropic mixture. In addition, the membrane separation method has the following advantages: no added chemical additive (extractant or azeotropic agent); the penetrating fluid (containing 5 to 50 mass percent of ethanol) directly returns to the rectifying tower, and almost no ethanol is lost (the average loss of the ethanol in the ordinary azeotropic rectification is 4 percent); no wastewater discharge; small heat energy consumption, small equipment volume, convenient operation and the like.
In which fig. 1 shows a schematic structural view of membrane separation, when a substance to be separated passes through a filtration membrane, a permeate permeates from the peripheral side, and a substance that cannot permeate from the membrane flows out as a retentate from an outlet.
Chitosan (CS for short), also called chitosan, has a chemical structure of β - (1 → 4) -2-amino-2-deoxy-D-glucose and contains-NH2and-OH, which is the membrane used for ethanol dehydration at first, but because of its low selectivity to water, the pure CS membrane has a low ethanol/water separation coefficient and a large permeability, so that the separation is incomplete, and it must be cross-linked, chemically modified and blended to improve its performance, so as to achieve better dehydration effect, and thus better used for water and ethanol separation. As shown in FIG. 2, the use of heteropolyacids (H) has been disclosed in the prior art14[NaP5W30O110]) CS (chitosan) was modified (j. phys. chem. c 2011,115, 14731-.
Similar to CS, currently available nanoporous polymer membranes do not have well-defined pore channels or uniform pore sizes on the nanometer scale to achieve clean molecular separations. And as the nano-pore size for separation becomes smaller, it becomes more difficult to manufacture a polymer filtration membrane of a small pore size. In addition, in view of the unfavorable separation effect of the existing anhydrous ethanol separation membrane, a new type of filtration membrane is urgently needed to achieve the clean separation of water and ethanol.
Disclosure of Invention
The invention aims to provide a graphene-alumina ceramic nano composite filter membrane, a filter, a preparation method and application thereof, wherein the graphene layer is formed on the alumina ceramic membrane to change the hydrophilic property of the alumina ceramic membrane, and the aperture of the nano composite filter membrane is controlled within the range of 1-2 nm, so that the aim of separating water and ethanol quickly, efficiently and cleanly is fulfilled.
In order to achieve the above object, the present invention provides a graphene-alumina ceramic nanocomposite filtration membrane, comprising an alumina ceramic membrane and a graphene layer located on at least one side surface of the alumina ceramic membrane; the aperture of the nano composite filtering membrane is about 1-2 nm.
Further, the alumina ceramic membrane is a tubular alumina ceramic membrane; the graphene layer is located on the outer surface of the tubular alumina ceramic membrane.
Further, the thickness of the graphene layer is 500 nm-1000 nm. The thickness of the graphene layer may affect the pore size of the nano composite filtration membrane, and thus the thickness of the graphene layer may be controlled within the above range.
Further, the graphene in the graphene layer is in a multilayer structure, for example, more than 1500 layers.
Further, the graphene layer is grown on at least one side surface of the alumina ceramic film by chemical vapor deposition.
Further, the graphene layer is grown on the outer surface of the tubular alumina ceramic membrane by chemical vapor deposition.
The invention also provides a method for preparing the graphene-alumina ceramic nano composite filter membrane, which comprises the following steps:
s1, arranging an alumina ceramic membrane;
s2, growing a graphene layer on at least one side surface of the alumina ceramic membrane in a chemical vapor deposition mode to obtain the graphene-alumina ceramic nano composite filtering membrane.
Further, the step S2 specifically includes: putting the silicon rubber and the alumina ceramic membrane into a tubular furnace; heating the reactor under the condition of inert gas (such as argon), wherein the heating rate is 0.5-2K/s (preferably 1K/s), adding hydrogen into the atmosphere when the temperature is 873K, and continuously keeping heating until the deposition temperature is reached (such as 1073K-1273K, specifically 1073K and 1273K); and (3) maintaining the flow and temperature conditions of the two gases to complete the growth of the graphene, so as to obtain the graphene-alumina ceramic nano composite filtering membrane.
Further, the thickness of graphene growth is controlled by the quality of the silicone rubber.
Wherein the flow rate of the inert gas (such as argon) is 250-350 sccm (such as 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350 sccm).
Wherein the flow rate of the hydrogen gas is 150-250 sccm (for example, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250 sccm).
Wherein the growth time of the graphene is 100 s-1500 s (for example, 100s, 120s, 150s, 200s, 250s, 300s, 400s, 500s, 600s, 700s, 800s, 900s, 1000s, 1100s, 1200s, 1300s, 1400s, 1500 s).
After the growth is finished, cooling to room temperature under the conditions of inert gas (such as argon) and hydrogen, and taking out to obtain the graphene-alumina ceramic nano composite filtering membrane.
The invention also provides a filter which is prepared from any one of the graphene-alumina ceramic nano composite filter membranes.
The invention also provides a method for concentrating or purifying the organic matter aqueous solution, wherein the concentrated organic matter aqueous solution or separated water and organic matters are obtained by enabling the organic matter aqueous solution to pass through the filter.
The organic substance is a water-soluble organic substance, and examples thereof include alcohols such as ethanol and methanol, and acids such as acetic acid, formic acid and propionic acid.
The invention has the beneficial effects that:
according to the invention, the graphene layer is loaded on the surface of the alumina ceramic membrane with uniform pore diameter, so that the hydrophilic property of the alumina ceramic membrane is changed, and the nano composite filtering membrane with enhanced hydrophobicity is obtained. The pore size of the nano composite filtering membrane is controlled to be about 1-2 nm by the graphene load amount, when water to be separated and organic matters (such as ethanol) or organic matter (such as ethanol) water solution to be concentrated pass through, the organic matters (such as ethanol) can smoothly pass through the nano composite filtering membrane by utilizing the hydrophilic and hydrophobic properties, and water molecules are intercepted, so that the aim of quickly, efficiently and cleanly separating the water from the organic matters (such as ethanol) or concentrating the organic matter (such as ethanol) water solution is fulfilled.
The nano composite filtering membrane provided by the invention has the advantages of good hydrophobicity, large flux, high interception rate, no blockage of the aperture of the membrane, effective interception of water molecules, pollution resistance and easy cleaning.
The preparation method of the nano composite filtering membrane provided by the invention is simple to operate, convenient and practical.
Drawings
FIG. 1 is a schematic diagram of a membrane separation in the prior art;
FIG. 2 shows the prior art using heteropolyacids (H)14[NaP5W30O110]) A membrane separation effect diagram after the chitosan is modified;
FIG. 3 is a photograph of a nano-composite filtration membrane of graphene-alumina ceramic prepared using the present invention to separate permeated water and ethanol;
fig. 4 is an SEM image of an uncoated graphene-coated bare alumina film prepared in example 1 of the present invention;
fig. 5 is an SEM image of the graphene-coated alumina ceramic nanocomposite filtration membrane prepared in example 1 of the present invention;
FIG. 6 is a Raman spectrum (20X) of the graphene-coated alumina ceramic nanocomposite filtration membrane prepared in example 1 of the present invention;
fig. 7 is a schematic structural view of a graphene-alumina ceramic nanocomposite filtration membrane of the present invention.
Detailed Description
As described above, the present invention provides a graphene-alumina ceramic nanocomposite filtration membrane for clean separation of water and ethanol. The nano composite filter membrane comprises an alumina ceramic membrane and a graphene layer positioned on the surface of at least one side of the alumina ceramic membrane; the aperture of the nano composite filtering membrane is about 1-2 nm.
Alumina is a common material with two properties of insulation and heat conduction, is commonly used as a filler additive, can be applied to insulating rubber to improve the mechanical strength of the rubber, and can also be applied to a plurality of purposes such as ceramics, insulating heat-conducting fillers, reinforced glass fillers, catalyst carriers and the like.
Graphene (RGO), the first time discovered in 2003, was a single-layer carbon atom film that was exfoliated from graphite material, yet it has electrical, optical, and mechanical properties that differ from those of graphite. The graphene adopted by the invention is a novel carbon material with a monolayer two-dimensional honeycomb lattice structure formed by tightly stacking monolayer carbon atoms, and has the advantages of stable structure, light transmission, strong flexibility, higher hardness than diamond and far higher electric conduction rate than a common conductor. The thickness of the graphite crystal film is only 0.335nm, and the graphite crystal film is a basic unit for constructing other dimension carbon materials and has excellent crystallinity and electrical property. The graphene has high theoretical specific surface area, outstanding heat conductivity and mechanical properties, and high electron mobility at room temperature. In addition, its special structure makes it have a series of properties such as half-integer quantum hall effect, never disappearing conductivity, and the like, and thus it is receiving attention. The graphene has the advantages of large specific surface area, high conductivity and the like, so that the graphene can be used as an electrode material, a sensor, a hydrogen storage material and the like.
According to the invention, graphene is used as a coating layer and is arranged on the alumina ceramic membrane for modifying the alumina ceramic, so that the prepared nano composite filtering membrane has strong hydrophobic property, and when a mixed solution of water and ethanol to be separated passes through the nano composite filtering membrane, the ethanol seeps out due to the hydrophobic property of the nano composite filtering membrane, thereby achieving the purpose of quickly and efficiently separating the water and the ethanol.
According to the invention, the pore size of the nano composite filtering membrane is about 1-2 nm. Taking ethanol as an example, although the water molecules can be regarded as spheres with the diameter of about 0.324nm and the diameter of the ethanol molecules is about 1nm, due to the hydrophobicity of the nano composite filtration membrane, when the mixed liquid of water and ethanol to be separated passes through, the water molecules are trapped, and the ethanol molecules can pass through smoothly, so that the purpose of separating the water from the ethanol is achieved.
According to the invention, the thickness of the graphene layer in the nano-composite ceramic membrane is 500 nm-1000 nm. The hydrophobicity of the nano composite filtering membrane is closely related to the thickness of the nano composite filtering membrane, and when the graphene coated on the alumina ceramic membrane is multilayer graphene, the nano composite filtering membrane has more excellent hydrophobicity compared with single-layer graphene.
The alumina ceramic membrane used in the present invention, particularly the tubular alumina ceramic membrane, may be a commercially available product.
The present invention will be described in further detail with reference to the following drawings and examples. However, those skilled in the art will appreciate that the scope of the present invention is not limited to the following examples. In light of the present disclosure, those skilled in the art will recognize that many variations and modifications may be made to the embodiments described above without departing from the spirit and scope of the present invention.
Example 1
The graphene-alumina ceramic nano composite filtering membrane is prepared by adopting a chemical vapor deposition method.
0.5 g of silicone rubber and an untreated tubular alumina ceramic membrane were placed in a tube furnace. Heating the reactor under argon at a heating rate of 1Ks-1The argon flow was 300 sccm. After the temperature rises to 873K, a certain amount of hydrogen gas (e.g., 200sccm) was started to be introduced into the atmosphere, and the temperature rise was continued until the deposition temperature (including 1073 and 1273K) was reached. Keeping the flow rate and the temperature conditions of the two gases for a certain time (including 120s and 1200s), and cooling the substrate to room temperature under the conditions of argon and hydrogen after the graphene grows, so as to obtain the graphene-alumina ceramic nano composite filtering membrane.
FIGS. 4 and 5 are SEM images of the tubular alumina ceramic membrane without any treatment and the nanocomposite filtration membrane prepared in the above example, comparing that a graphene layer is formed on the surface of the alumina ceramic membrane; the attachment of the graphene layer to the ceramic membrane surface can be further illustrated by fig. 6. In addition, as can be seen in conjunction with the schematic illustration of fig. 7, pore size control of the nanocomposite filtration membrane is achieved.
Example 2
The growth thickness of the graphene is controlled by the quality of the silicon rubber. Specifically, graphene layers having different thicknesses (500nm to 1000nm) can be obtained as needed by adjusting the amount of the silicone rubber in the same manner as in example 1.
Example 3
When the graphene-alumina ceramic nanocomposite filter membranes of examples 1-2 were used for separating ethanol from water, the separation process can be seen in fig. 3, and the separation effect reached about 95%.
Claims (18)
1. A graphene-alumina ceramic nano composite filter membrane is characterized by comprising an alumina ceramic membrane and a graphene layer positioned on the surface of at least one side of the alumina ceramic membrane; the aperture size of the nano composite filtering membrane is 1-2 nm;
the thickness of the graphene layer is 500 nm-1000 nm;
the graphene in the graphene layer is of a multilayer structure and is more than 1500 layers.
2. The nanocomposite filtration membrane according to claim 1, wherein the alumina ceramic membrane is a tubular alumina ceramic membrane; the graphene layer is located on the outer surface of the tubular alumina ceramic membrane.
3. The nanocomposite filtration membrane according to claim 1, wherein the graphene layer is grown by chemical vapor deposition on at least one side surface of an alumina ceramic membrane.
4. The nanocomposite filtration membrane according to claim 3, wherein the graphene layer is grown by chemical vapor deposition on the outer surface of the tubular alumina ceramic membrane.
5. The nanocomposite filtration membrane according to claim 1, wherein the nanocomposite filtration membrane is produced by a process comprising the steps of:
s1, arranging an alumina ceramic membrane;
s2, putting the silicon rubber and the alumina ceramic membrane into a tube furnace; heating the reactor under the condition of inert gas, wherein the heating rate is 0.5-2K/s, adding hydrogen in the atmosphere when the temperature is 873K, and continuously keeping heating until the deposition temperature is 1073K-1273K; and (3) maintaining the flow and temperature conditions of the two gases to complete the growth of the graphene, so as to obtain the graphene-alumina ceramic nano composite filtering membrane.
6. A method for preparing a nanocomposite filtration membrane of graphene-alumina ceramic according to claim 1, comprising the steps of:
s1, arranging an alumina ceramic membrane;
s2, putting the silicon rubber and the alumina ceramic membrane into a tube furnace; heating the reactor under the condition of inert gas, wherein the heating rate is 0.5-2K/s, adding hydrogen in the atmosphere when the temperature is 873K, and continuously keeping heating until the deposition temperature is 1073K-1273K; and (3) maintaining the flow and temperature conditions of the two gases to complete the growth of the graphene, so as to obtain the graphene-alumina ceramic nano composite filtering membrane.
7. The method of claim 6, wherein in step S2, the inert gas is argon.
8. The method according to claim 6, wherein in step S2, the temperature increase rate is 1K/S.
9. The method according to claim 6, wherein in step S2, the deposition temperature is 1073K or 1273K.
10. The method according to claim 6, wherein in step S2, the thickness of the graphene growth is controlled by the quality of the silicon rubber.
11. The method as claimed in claim 6, wherein the inert gas has a flow rate of 250 to 350sccm in step S2.
12. The method as claimed in claim 6, wherein the flow rate of the hydrogen gas is 150 to 250sccm in step S2.
13. The method according to claim 6, wherein in the step S2, the graphene is grown for 100S-1500S.
14. The method according to claim 6, wherein in step S2, after the growth is completed, the membrane is cooled to room temperature under inert gas and hydrogen, and then taken out to obtain the graphene-alumina ceramic nano composite filtration membrane.
15. A filter produced from the graphene-alumina ceramic nanocomposite filtration membrane according to any one of claims 1 to 5.
16. A method for concentrating or purifying an organic aqueous solution, comprising passing the organic aqueous solution through the filter according to claim 15 to obtain a concentrated organic aqueous solution or to obtain separated water and organic substances.
17. The method for concentrating or purifying an organic aqueous solution according to claim 16, wherein the organic substance is a water-soluble organic substance.
18. The method for concentrating or purifying an organic aqueous solution according to claim 17, wherein the organic substance is ethanol, methanol, acetic acid, formic acid, or propionic acid.
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| CN109400203A (en) * | 2018-12-29 | 2019-03-01 | 厦门凯纳石墨烯技术股份有限公司 | A kind of preparation method of graphene inorganic porous ceramic film |
| CN111569669A (en) * | 2020-05-09 | 2020-08-25 | 云南电网有限责任公司电力科学研究院 | Modified super-hydrophobic epoxy resin composite membrane and preparation method thereof |
| CN112807743B (en) * | 2021-01-15 | 2023-03-24 | 江苏普利瑞科技有限公司 | Method for concentrating brine and separating organic matters by using extraction liquid |
| CN115385724A (en) * | 2022-05-18 | 2022-11-25 | 北京石墨烯研究院 | Modified ceramic separation membrane and preparation method thereof |
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