CN114130207B - Multifunctional total heat exchange membrane and preparation method thereof - Google Patents

Multifunctional total heat exchange membrane and preparation method thereof Download PDF

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CN114130207B
CN114130207B CN202111384153.7A CN202111384153A CN114130207B CN 114130207 B CN114130207 B CN 114130207B CN 202111384153 A CN202111384153 A CN 202111384153A CN 114130207 B CN114130207 B CN 114130207B
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heat exchange
total heat
exchange membrane
graphene
graphene oxide
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CN114130207A (en
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牛静
梁凤
陈美平
李景霞
张水
殷晓冬
许利娟
殷晓东
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Zhongke Langmai Technology Co ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0001—Making filtering elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
    • B01D46/0028—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions provided with antibacterial or antifungal means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
    • B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/22—Thermal or heat-resistance properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/48—Antimicrobial properties

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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
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  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The application relates to the technical field of heat exchange membranes, and particularly discloses a multifunctional total heat exchange membrane and a preparation method thereof. The exchange membrane mainly comprises graphene, graphene oxide, ionic liquid and a high-molecular polymer, wherein the mass ratio of the graphene to the graphene oxide to the ionic liquid to the high-molecular polymer is as follows: 1-2: 1 to 6:1 to 5:10 to 30 percent. The application has the advantages that: the total heat exchange efficiency, the sterilization and mildew prevention effects, the mechanical strength and the service life of the total heat exchange membrane are improved.

Description

Multifunctional total heat exchange membrane and preparation method thereof
Technical Field
The application relates to the technical field of heat exchange membranes, in particular to a multifunctional total heat exchange membrane and a preparation method thereof.
Background
In recent years, with successive outbreaks of SARS coronavirus, MERS coronavirus, and novel coronavirus, the transmissibility of viruses has been gradually increased, and the viruses can be transmitted through various routes such as aerosol, air, and contact. Therefore, air purification becomes critical.
The fresh air system can effectively improve the indoor air quality problem of closed spaces such as markets, supermarkets and office buildings, and reduce and inhibit the occurrence probability of related diseases. The fresh air system for total heat exchange can exchange energy and humidity on the total heat exchange membrane through external fresh air and discharged polluted air while keeping indoor air circulation and obtaining fresh air, and meanwhile, the external air is filtered and purified, so that the indoor air quality is ensured, and the energy-saving effect is remarkable.
In summary, the heat exchange material becomes a key factor affecting the heat exchange of indoor air and the air quality. However, the membrane material used by the current enterprises has lower heat recovery rate, does not have the effects of antibiosis and mildew resistance, has larger energy consumption in the long-term use process, and simultaneously the wet air causes enrichment of bacteria on the surface of the membrane, so that the service life of the membrane material is reduced, and secondary pollution is easily caused.
Disclosure of Invention
In order to improve the sterilization and mildew-proof effects of the total heat exchange membrane, the application provides a multifunctional total heat exchange membrane and a preparation method thereof.
In a first aspect, the present application provides a multifunctional total heat exchange membrane, which adopts the following technical scheme:
the multifunctional total heat exchange membrane mainly comprises graphene, graphene oxide, ionic liquid and high molecular polymer, wherein the mass ratio of the graphene to the graphene oxide to the ionic liquid to the high molecular polymer is as follows: 1-2: 1 to 6:1 to 5:10 to 30 percent.
By adopting the technical scheme, the graphene is formed by sp 2 A honeycomb structure single-layer two-dimensional carbon nano material composed of hybridized carbon atoms. Each carbon atom passing through 3 sp 2 The hybridized orbitals form 3 sigma bonds to 3 other carbon atoms and 12 p electrons of the carbon atoms used form a delocalized large pi-bond planar honeycomb structure, the structure of which imparts many unique properties thereto. It has a high theoretical specific surface area (2630 m 2 g -1 ) High intrinsic mobility (200000 cm) 2 v -1 s -1 ) High Young's modulus (about 1.0 TPa) and high thermal conductivity (about 5000 Wm) -1 K -1 ) High optical transmittance (-97.7%) and high electrical conductivity. Research shows that carbon atoms in the intrinsic hydrophobic graphite structure provide effective adsorption sites for water vapor, and that the electric neutrality of the surface is not beneficial to the adhesion of pollutants, so that the anti-pollution performance of the membrane material is improved, and finally, the sharp edges of the sheet layers can damage the structure of bacteria and influence the metabolism of the bacteria through mechanical damage.
Graphene oxide is used as a derivative of graphene, has a unique two-dimensional structure, and the surface of the graphene oxide is rich in oxygen-containing groups. Hydrophilic oxygen-containing groups provide adsorption sites for more water molecules, with good water adsorption. In addition, the charging of the oxygen-containing group can lead the oxygen-containing group to enter the microorganism after interacting with the microorganism, so that the metabolism balance of the microorganism free radicals is deregulated, and the biological film and the macromolecular substance are subjected to peroxidation damage, thereby achieving the antibacterial effect. Therefore, graphene oxide not only has good water absorption, but also can kill bacteria through a lamellar structure and oxygen-containing groups.
The ionic liquid is a green solvent which is not easy to volatilize, stable and flammable, is completely composed of positively charged cations and negatively charged anions, is in a liquid state at room temperature, and has good heat conductivity, antibacterial property and anti-pollution property due to rich charged groups.
The addition of the high molecular polymer has the following advantages: firstly, the synergistic antibacterial and anti-pollution effects among graphene, graphene oxide and ionic liquid are improved; secondly, the high molecular polymer and graphene or graphene oxide material form effective chemical bond connection of hydrogen bond, ionic bond and/or covalent bond through polar group functional groups, and the combination of the graphene and the graphene oxide is stable and uniformly dispersed by adding the high molecular polymer, so that the uniformity and mechanical strength of the prepared exchange membrane are effectively improved, and meanwhile, a water permeable channel is formed inside the total heat exchange membrane, so that the selective water permeability of the total heat exchange membrane is realized, the water vapor permeability of the total heat exchange membrane is improved, and the latent heat recovery efficiency is enhanced; finally, the use of the high molecular polymer can improve the compactness and the sterilization effect of the exchange membrane, and the prepared exchange membrane is a compact membrane, so that dust particles in the air can be effectively trapped on the basis of effectively killing bacteria, mold and viruses in the air.
Through intensive researches of the inventor, the membrane with sterilization, mildew resistance, high mechanical strength and high heat exchange efficiency can be developed by adopting graphene, graphene oxide, ionic liquid and high-molecular polymer to be mixed according to a certain proportion.
Preferably, the mass ratio of the graphene to the graphene oxide is 1:1 to 3.
By adopting the technical scheme, the prepared total heat exchange membrane is promoted to have good sterilization and mildew-proof effects by adopting the combination of the graphene and the graphene oxide in the proportion.
Preferably, the graphene has at least one of a size of 100-200nm, 1-2 μm, and 5-10 μm.
Preferably, the graphene oxide has at least one of the dimensions of 100-200nm, 1-2 μm and 5-10 μm, and the content of oxygen-containing groups of the graphene oxide is 10% -40%.
Through adopting above-mentioned technical scheme, adopt above-mentioned horizontal size's graphite alkene and graphene oxide to and graphene oxide's oxygen-containing group is between 10% -40%, not only can guarantee the degree of densification of full heat exchange membrane, but also have better antibacterial effect.
Preferably, the high molecular polymer is at least one of polyvinyl alcohol, polyacrylamide, polyethylene glycol, chitosan, cellulose acetate and sodium alginate.
Preferably, the molecular weight of the high molecular polymer is 1.5-70 kDa.
Through adopting above-mentioned technical scheme, adopt above-mentioned polymer and graphene, graphene oxide, ionic liquid to combine, the total heat exchange membrane of preparation not only heat exchange efficiency is high, disinfect, mould-proof, can filter the dust in the air simultaneously, but also mechanical properties is high, life is longer, but reuse has reduced manufacturing and use cost.
Preferably, the ionic liquid is any one or more of 1-ethyl-3-methylimidazolium tetrafluoroboric acid, 1-butyl-3-methylimidazolium chloric acid and 1- (3-hydroxypropyl) -3-methylimidazolium tetrafluoroboric acid.
By adopting the technical scheme, the performance of the prepared total heat exchange membrane can be obviously improved by adopting the ionic liquid: (1) The ionic liquid is a stable green solvent, and can ensure uniform dispersion of graphene, graphene oxide and polymers; (2) The graphene, the graphene oxide, the ionic liquid and the polymer are synergistic by utilizing multiple sterilization mechanisms such as mechanical damage, radical action, mechanical wrapping and the like, so that the antibacterial performance of the prepared total heat exchange membrane is improved; (3) The ionic liquid is introduced to increase the number of ionic groups in the membrane, so that the moisture permeability and enthalpy exchange efficiency of the membrane can be effectively improved.
In a second aspect, the present application provides a method for preparing a multifunctional total heat exchange membrane, which adopts the following technical scheme:
a preparation method of a multifunctional total heat exchange membrane comprises the following steps:
dispersing graphene and graphene oxide in a solvent according to a certain proportion, and carrying out ultrasonic treatment for 0.5-3 hours to uniformly disperse the graphene and the graphene oxide; step two, adding a proper amount of ionic liquid into the solution in the step one, and uniformly stirring;
step three, adding a proper amount of high molecular polymer into the solution in the step two, uniformly stirring, defoaming and standing;
and fourthly, scraping the solution obtained in the third step on a substrate, drying for 20-24 hours, heating, and finally stripping from the substrate to obtain the total heat exchange film with a certain thickness.
Preferably, the total heat exchange membrane has a thickness of 1 to 200 μm.
Preferably, the solvent is one or more of water, methanol, ethanol, acetone and N-N dimethylformamide.
Preferably, the substrate is one of a glass plate, a silicon wafer and a metal plate.
According to the technical scheme, graphene and graphene oxide are uniformly dispersed in a solvent in an ultrasonic treatment mode, then ionic liquid is added for stirring, and finally a high-molecular polymer is added for stirring, so that all components in the solution can be uniformly dispersed; then the solution is scraped on the substrate to obtain the total heat exchange membrane with the thickness of 1-200 mu m. The preparation method is simple and easy for industrial production, and the multifunctional total heat exchange membrane prepared by the method has the advantages of remarkably improved antibacterial and mildew-proof capabilities, high heat conductivity coefficient, higher mechanical strength, greatly prolonged service life, high water vapor transmission rate, high latent heat recovery efficiency, and capability of filtering and preventing the spread of large particles such as dust in outdoor air.
Preferably, the heating treatment is carried out at 25-60 ℃ for 6-12 hours.
By adopting the technical scheme, the heat treatment temperature is lower than 25 ℃, the drying time is longer, and when the temperature is higher than 60 ℃, the damage of the total heat exchange membrane is easy to occur, and the performance of the total heat exchange membrane is influenced. Through the research of the inventor, the heat treatment temperature can be adopted to quickly dry and mold the total heat exchange membrane, and simultaneously, the damage of the heat treatment to the total heat exchange membrane is reduced.
In summary, the present application has the following beneficial effects:
1. according to the invention, the graphene oxide, the ionic liquid and the polymer are compounded, so that the water vapor transmission capacity is enhanced, and the total heat exchange efficiency is improved.
2. The composite of graphene, graphene oxide and ionic liquid promotes the prepared total heat exchange membrane to have good sterilization and mildew-proof effects.
3. The total heat exchange membrane prepared by the invention not only can sterilize and resist mildew, but also has high heat exchange efficiency, and can filter dust in the air.
4. The total heat exchange membrane prepared by the invention has high mechanical property and longer service life, can be reused, and reduces the production and use costs;
5. the preparation method is simple and is easy for industrial production.
Detailed Description
The present application is described in further detail below with reference to examples.
The raw materials used in the present application are all commercially available.
Examples
Example 1
A multifunctional total heat exchange membrane is prepared by the following method:
2g of graphene powder (transverse dimension 1-2 mu m), 2g of graphene oxide (transverse dimension 1-2 mu m, oxygen-containing group content 40%) are added into a mixed solvent of 500g of water and 500g of ethanol, ultrasonic treatment (600W) is carried out for 3 hours, so that the graphene powder is completely and uniformly dispersed, 5g of 1- (3-hydroxypropyl) -3-methylimidazole tetrafluoroboric acid is taken and uniformly stirred, 25g of chitosan (molecular weight 10 kDa) is added, and standing and defoaming are carried out after uniform stirring.
The casting solution was knife coated on a glass plate, dried for 24 hours, and then treated at 60℃for 12 hours. The resultant was peeled off to obtain a total heat exchange membrane having a thickness of 60. Mu.m.
Example 2
A multifunctional total heat exchange membrane is prepared by the following method:
1.34g of graphene powder (transverse dimension 1-2 mu m), 2.66g of graphene oxide (transverse dimension 1-2 mu m, oxygen-containing group content 40%) are added into a mixed solvent of 500g of water and 500g of ethanol, ultrasonic treatment (600W) is carried out for 3 hours to ensure that the graphene powder is completely and uniformly dispersed, 5g of 1- (3-hydroxypropyl) -3-methylimidazole tetrafluoroboric acid is taken and uniformly stirred, 25g of chitosan (molecular weight 10 kDa) is added, and the mixture is stirred uniformly and then left to stand for deaeration.
The casting solution was knife coated on a glass plate, dried for 24 hours, and then treated at 60℃for 12 hours. The resultant was peeled off to obtain a total heat exchange membrane having a thickness of 60. Mu.m.
Example 3
A multifunctional total heat exchange membrane is prepared by the following method:
1g of graphene powder (transverse dimension 1-2 mu m), 3g of graphene oxide (transverse dimension 1-2 mu m, oxygen-containing group content 40%) are added into a mixed solvent of 500g of water and 500g of ethanol, ultrasonic treatment (600W) is carried out for 3 hours, so that the graphene powder is completely and uniformly dispersed, 5g of 1- (3-hydroxypropyl) -3-methylimidazole tetrafluoroboric acid is taken and uniformly stirred, 25g of chitosan (molecular weight 10 kDa) is added, and standing and defoaming are carried out after the uniform stirring.
The casting solution was knife coated on a glass plate, dried for 24 hours, and then treated at 60℃for 12 hours. The resultant was peeled off to obtain a total heat exchange membrane having a thickness of 60. Mu.m.
Example 4
A multifunctional total heat exchange membrane is prepared by the following method:
2g of graphene powder (with the transverse dimension of 1-2 mu m), 6g of graphene oxide (with the transverse dimension of 1-2 mu m and the oxygen-containing group content of 40%) are added into a mixed solvent of 500g of water and 500g of ethanol, the mixed solvent is treated by ultrasonic (600W) for 3 hours to ensure that the mixed solvent is completely and uniformly dispersed, 3g of 1-butyl-3-methylimidazole chloric acid is taken and uniformly stirred, 10g of cellulose acetate (with the molecular weight of 1.5 kDa) is added, and the mixed solution is left to stand for deaeration after uniform stirring.
The casting solution was knife coated on a glass plate, dried for 24 hours, and then treated at 60℃for 12 hours. The resultant was peeled off to obtain a total heat exchange membrane having a thickness of 60. Mu.m.
Example 5
A multifunctional total heat exchange membrane is prepared by the following method:
2g of graphene powder (with the transverse dimension of 1-2 mu m), 1g of graphene oxide (with the transverse dimension of 1-2 mu m and the oxygen-containing group content of 40%) are added into a mixed solvent of 500g of water and 500g of ethanol, the mixed solvent is treated by ultrasonic (600W) for 3 hours to ensure that the mixed solvent is completely and uniformly dispersed, 1g of 1-butyl-3-methylimidazole tetrafluoroboric acid is taken and uniformly stirred, 20g of sodium alginate (with the molecular weight of 40 kDa) is added, and the mixed solution is left to stand for deaeration after being uniformly stirred.
The casting solution was knife coated on a glass plate, dried for 24 hours, and then treated at 60℃for 12 hours. The resultant was peeled off to obtain a total heat exchange membrane having a thickness of 60. Mu.m.
Example 6
A multifunctional total heat exchange membrane is prepared by the following method:
2g of graphene powder (transverse dimension 1-2 mu m), 1g of graphene oxide (transverse dimension 1-2 mu m, oxygen-containing group content 40%) are added into a mixed solvent of 500g of water and 500g of ethanol, ultrasonic treatment (600W) is carried out for 3 hours, so that the graphene powder is completely and uniformly dispersed, 1g of 1-ethyl-3-methylimidazole tetrafluoroboric acid is taken and uniformly stirred, 30g of polyacrylamide (molecular weight 70 kDa) is added, and standing and defoaming are carried out after uniform stirring.
The casting solution was knife coated on a glass plate, dried for 24 hours, and then treated at 60℃for 12 hours. The resultant was peeled off to obtain a total heat exchange membrane having a thickness of 60. Mu.m.
Example 7
A multifunctional total heat exchange membrane is prepared by the following method:
2g of graphene powder (with the transverse dimension of 100-200 nm), 2g of graphene oxide (with the transverse dimension of 100-200nm and the oxygen-containing group content of 40%) are added into a mixed solvent of 500g of water and 500g of ethanol, the mixed solvent is treated by ultrasonic (600W) for 3 hours to ensure that the mixed solvent is completely and uniformly dispersed, 5g of 1- (3-hydroxypropyl) -3-methylimidazole tetrafluoroboric acid is taken and uniformly stirred, 25g of chitosan (with the molecular weight of 10 kDa) is added, and the mixed solution is left to stand for deaeration after being uniformly stirred.
The casting solution was knife coated on a glass plate, dried for 24 hours, and then treated at 60℃for 24 hours. The resultant was peeled off to obtain a total heat exchange membrane having a thickness of 60. Mu.m.
Example 8
A multifunctional total heat exchange membrane is prepared by the following method:
2g of graphene powder (with the transverse dimension of 5-10 mu m), 2g of graphene oxide (with the transverse dimension of 5-10 mu m and the oxygen-containing group content of 40%) are added into a mixed solvent of 500g of water and 500g of ethanol, the mixed solvent is treated by ultrasonic (600W) for 3 hours to ensure that the mixed solvent is completely and uniformly dispersed, 5g of 1- (3-hydroxypropyl) -3-methylimidazole tetrafluoroboric acid is taken and uniformly stirred, 25g of chitosan (with the molecular weight of 10 kDa) is added, and the mixed solution is left to stand for deaeration after uniform stirring.
The casting solution was knife coated on a glass plate, dried for 24 hours, and then treated at 60℃for 12 hours. The resultant was peeled off to obtain a total heat exchange membrane having a thickness of 60. Mu.m.
Example 9
A multifunctional total heat exchange membrane is prepared by the following method:
2g of graphene powder (transverse dimension 1-2 mu m), 2g of graphene oxide (transverse dimension 1-2 mu m, oxygen-containing group content 25%) are added into a mixed solvent of 500g of water and 500g of ethanol, ultrasonic treatment (600W) is carried out for 3 hours, so that the graphene powder is completely and uniformly dispersed, 5g of 1- (3-hydroxypropyl) -3-methylimidazole tetrafluoroboric acid is taken and uniformly stirred, 25g of chitosan (molecular weight 10 kDa) is added, and standing and defoaming are carried out after the uniform stirring.
The casting solution was knife coated on a glass plate, dried for 24 hours, and then treated at 60℃for 12 hours. The resultant was peeled off to obtain a total heat exchange membrane having a thickness of 60. Mu.m.
Example 10
A multifunctional total heat exchange membrane is prepared by the following method:
2g of graphene powder (transverse dimension 1-2 mu m), 2g of graphene oxide (transverse dimension 1-2 mu m, oxygen-containing group content 10%) are added into a mixed solvent of 500g of water and 500g of ethanol, ultrasonic treatment (600W) is carried out for 3 hours, so that the graphene powder is completely and uniformly dispersed, 5g of 1- (3-hydroxypropyl) -3-methylimidazole tetrafluoroboric acid is taken and uniformly stirred, 25g of chitosan (molecular weight 10 kDa) is added, and standing and defoaming are carried out after uniform stirring.
The casting solution was knife coated on a glass plate, dried for 24 hours, and then treated at 60℃for 12 hours. The resultant was peeled off to obtain a total heat exchange membrane having a thickness of 60. Mu.m.
Comparative example
Comparative example 1
Comparative example 1 differs from example 1 in that no graphene powder was added.
Comparative example 2
Comparative example 2 differs from example 1 in that graphene oxide was not added.
Comparative example 3
Comparative example 3 is different from example 1 in that the amount of graphene oxide added was 10g.
Comparative example 4
Comparative example 4 is different from example 1 in that the amount of graphene oxide added was 0.5g.
Comparative example 5
Comparative example 5 is different from example 1 in that the added amount of graphene powder is 0.5g.
Comparative example 6
Comparative example 6 is different from example 1 in that the amount of graphene powder added was 4g.
Comparative example 7
Comparative example 7 differs from example 1 in that 1- (3-hydroxypropyl) -3-methylimidazolium tetrafluoroboric acid was not added.
Comparative example 8
Comparative example 8 differs from example 1 in that no chitosan was added.
Performance test
Detection method
(1) Filtration test
And (3) testing the air filtering performance, namely testing the filtering performance of the test piece by adopting a filter material comprehensive performance test table. Wherein the test particle size is 0.3 μm, and the filtration efficiency (η,%) is calculated as η= (1-p) ×100%. Wherein p is the transmittance of the composite filter material to particles,%.
(2) Steam experiment
The moisture permeability of the films was measured at 23℃and 50% relative humidity.
The film was suitably cut to an area of 12.56cm 2 The moisture permeability of the films was measured at 23℃and 50% relative humidity in a plate assembly.
(3) Total heat exchange efficiency test
The film was suitably cut to an area of 12.56cm 2 Placing the fresh air into a flat plate assembly, wherein the fresh air temperature is 35 ℃ and RH 60%; the exhaust temperature is 25 ℃ and RH is 35 percent.
(4) The concentration of the sterilization experiment is 10 8 cfu/ml of E.coli (ATCC 11229) suspension, the area of the experimental group is 12.56cm 2 The control group is a common plastic film with the same area, 10ml of bacterial suspension is respectively and uniformly sprayed, and after 1h, the sterilization rate is measured.
(5) Tensile test
After conditioning at 23℃for 24 hours with a relative humidity of 50%, the stretching speed was 1mm/min at a test width of 100mm, a test length of 100mm and a test length of 100mm in the flow direction.
TABLE 1 results of the tests in examples 1-10 and comparative examples 1-8
In table 1, "-" indicates that no evaluation was made (comparative example 8 to which no chitosan was added did not have a film).
It can be found in combination with examples 1 to 10 and comparative examples 1 to 8 and with Table 1 that 2g of graphene powder (transverse dimension 1 to 2 μm), 2g of graphene oxide (transverse dimension 1 to 2 μm, oxygen-containing group content 40%), 5g of 1- (3-hydroxypropyl) -3-methylimidazolium tetrafluoroboric acid, 25g of chitosan (molecular weight 10 kDa) are the optimal compositions for producing excellent membranes of total heat exchange materials. At this time, the membrane had a filtration efficiency of 99% and a moisture permeability of 3784g/m 2 D, sensible heat exchange efficiency is 87.2%, enthalpy exchange efficiency is 69.8%, sterilization rate is 95.8%, and tensile strength is 36.8Mpa. The total heat exchange membrane can realize dust filtration in air, high-efficiency exchange of temperature and humidity, and has antibacterial and mildew-proof properties and good mechanical strength.
As can be seen from examples 1 to 3 and comparative examples 1 to 6 in combination with table 1, both graphene and graphene oxide have a certain thermal conductivity and bactericidal properties, but compared with graphene oxide, the thermal conductivity of graphene is better than that of graphene oxide, and the bactericidal effect of graphene oxide is better than that of graphene due to the presence of oxygen-containing groups, and the effect is optimal when the ratio of graphene to graphene oxide is 1:1.
From examples 1, 4-6 and comparative example 8, in combination with Table 1, the main function of the high molecular polymer is to ensure the mechanical property and filtration efficiency of the total heat exchange membrane, and the proper polymer mass and molecular weight are used to facilitate the construction of a compact and defect-free total heat exchange material membrane, realize the filtration and interception of dust in the air, and ensure the good mechanical property and longer service life of the total heat exchange material membrane; as can be seen from comparative example 8, the film cannot be formed without adding a high molecular polymer.
As can be seen from examples 1, 4 to 6 and comparative example 7 in combination with table 1, the presence of the ionic liquid mainly enhances the number of ionic groups to enhance the thermal conductivity of the sensible heat exchange membrane material and increases the water molecule permeation amount to enhance the enthalpy exchange efficiency. In addition, the increased number of ionic groups increases the sterilization strength.
From examples 7-10, in combination with Table 1, it can be seen that graphene and graphene oxide are not the better the larger the lateral dimension, the higher the added quality. The reason may be that the sizes of the graphene and the graphene oxide are too large or the addition quality is too high, so that the prepared total heat exchange membrane is not uniform, and macropores are formed, so that the filtration sterilization performance is reduced. The higher the oxidation degree of the graphene oxide is, the more binding sites are formed, so that the graphene, the ionic liquid and the high-molecular polymer are uniformly distributed, and the compactness degree and the sterilization performance of the total heat exchange membrane are improved.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims (8)

1. A multifunctional total heat exchange membrane is characterized in that: the exchange membrane mainly comprises graphene, graphene oxide, ionic liquid and a high-molecular polymer, wherein the mass ratio of the graphene to the graphene oxide to the ionic liquid to the high-molecular polymer is as follows: 1-2: 1 to 6:1 to 5:10 to 30 percent;
the ionic liquid is any one or more of 1-ethyl-3-methylimidazole tetrafluoroboric acid, 1-butyl-3-methylimidazole chloric acid and 1- (3-hydroxypropyl) -3-methylimidazole tetrafluoroboric acid;
the high molecular polymer is at least one of polyvinyl alcohol, polyacrylamide, polyethylene glycol, chitosan, cellulose acetate and sodium alginate;
firstly, uniformly dispersing graphene and graphene oxide in a solvent in an ultrasonic treatment mode, then adding an ionic liquid for stirring, and finally adding a high-molecular polymer for stirring, so that all components in the solution can be uniformly dispersed; then the solution is scraped on the substrate to obtain the total heat exchange membrane with the thickness of 1-200 mu m.
2. A multifunctional total heat exchange membrane according to claim 1, characterized in that: the mass ratio of the graphene to the graphene oxide is 1:1 to 3.
3. A multifunctional total heat exchange membrane according to claim 1, characterized in that: the graphene has at least one of a size of 100-200nm, 1-2 μm and 5-10 μm.
4. A multifunctional total heat exchange membrane according to claim 1, characterized in that: the graphene oxide has at least one of the dimensions of 100-200nm, 1-2 mu m and 5-10 mu m, and the oxygen-containing group content of the graphene oxide is 10% -40%.
5. A multifunctional total heat exchange membrane according to claim 1, characterized in that: the molecular weight of the high molecular polymer is 1.5-70 kDa.
6. A method for preparing a multifunctional total heat exchange membrane according to any one of claims 1 to 5, comprising the steps of:
dispersing graphene and graphene oxide in a solvent according to a certain proportion, and carrying out ultrasonic treatment for 0.5-3 hours to uniformly disperse the graphene and the graphene oxide;
step two, adding a proper amount of ionic liquid into the solution in the step one, and uniformly stirring;
step three, adding a proper amount of high molecular polymer into the solution in the step two, uniformly stirring, defoaming and standing;
and fourthly, scraping the solution obtained in the third step on a substrate, drying for 20-24 hours, heating, and finally stripping from the substrate to obtain the total heat exchange film with a certain thickness.
7. The method for preparing the multifunctional total heat exchange membrane according to claim 6, wherein the method comprises the following steps: the solvent is one or more of water, methanol, ethanol, acetone and N-N dimethylformamide.
8. The method for preparing the multifunctional total heat exchange membrane according to claim 6, wherein the method comprises the following steps: the heating treatment condition is 25-60 ℃ and the treatment time is 6-12 h.
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