CN115282782A - Total heat exchange membrane doped with functionalized ZIF-7 nanoparticles and preparation method thereof - Google Patents

Total heat exchange membrane doped with functionalized ZIF-7 nanoparticles and preparation method thereof Download PDF

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CN115282782A
CN115282782A CN202210741057.1A CN202210741057A CN115282782A CN 115282782 A CN115282782 A CN 115282782A CN 202210741057 A CN202210741057 A CN 202210741057A CN 115282782 A CN115282782 A CN 115282782A
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zif
nanoparticles
functionalized
membrane
heat exchange
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薛立新
白超杰
张祚群
苌现
高扬
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Zhejiang University of Technology ZJUT
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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
    • 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
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/04—Tubular 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
    • B01D69/06—Flat 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
    • B01D69/08—Hollow fibre 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F12/00—Use of energy recovery systems in air conditioning, ventilation or screening
    • F24F12/001—Use of energy recovery systems in air conditioning, ventilation or screening with heat-exchange between supplied and exhausted air
    • F24F12/006—Use of energy recovery systems in air conditioning, ventilation or screening with heat-exchange between supplied and exhausted air using an air-to-air heat exchanger
    • 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

Abstract

The invention discloses a full heat exchange membrane doped with functionalized ZIF-7 nano particles, which comprises an ultrafiltration membrane supporting layer, a polyamide separation layer and functionalized ZIF-7 nano particles; the polyamide separation layer is distributed on the surface and in the holes of the ultrafiltration membrane support layer; the functionalized ZIF-7 nanoparticles are distributed in the polyamide separation layer. According to the invention, the ligand structure of the ZIF-7 nano particle is regulated and controlled to realize the functionalization of the ZIF-7 nano particle, and the functionalized ZIF-7 particle is successfully added in the interfacial polymerization process. The preparation method has the advantages that the functionalized ZIFs nanoparticles are doped in the polyamide separation layer, so that the interaction force of a phase interface can be effectively regulated and controlled, the interface gap is avoided, a rapid transmission selective micro channel is accurately constructed, the mechanical property of the membrane is increased, the surface roughness of the membrane is increased, the surface area of the separation layer is increased, and the moisture permeability, the air resistance and the heat recovery efficiency are improved.

Description

Total heat exchange membrane doped with functionalized ZIF-7 nanoparticles and preparation method thereof
Technical Field
The invention belongs to the fields of moisture and gas permeation and heat recovery, and particularly relates to a full heat exchange membrane doped with functionalized ZIF-7 nanoparticles and a preparation method thereof.
Background
Nearly one third of the electricity energy consumption in China is used for residential buildings and shopping malls, and nearly half of the electricity is used for air conditioners. In addition, people spend more than 80% of their time indoors, so ventilation is of paramount importance during the frequent use of air conditioners. From the viewpoint of energy conservation, environmental protection and body health, the ventilation system using the total heat exchange energy-saving principle plays an important role in keeping the human health and saving energy. While the quality of indoor air is improved by exchanging indoor polluted air (such as harmful gases like carbon dioxide and formaldehyde) with outdoor fresh air, in order to reduce the energy required for adjusting the temperature of the fresh air, scientists design a total heat exchanger as a core device of an energy-saving fresh air system to recover energy between the outdoor fresh air and the indoor polluted air. With the rapid development of membrane technology, the full heat exchanger taking the membrane as the heat recovery medium can achieve good energy recovery and gas (such as CO) under the premise of ensuring the ventilation effect under the modification of the ZIF-containing nano particles 2 ) Barrier effect.
The total heat exchanger is used for obtaining high-efficiency recovery through sensible heat exchange and latent heat exchange by taking a total heat exchange membrane as a medium. Sensible heat exchange has no mass transfer process, and only fresh air and exhaust air are transferred through energy, so that the temperature is changed; the latent heat exchange is the water vapor mass exchange between the fresh air and the exhaust air, so that the concentration of water vapor in the air is adjusted, the latent heat of the water vapor is increased or reduced, and the purpose of energy conservation is achieved. The energy density in the humid air is large because the latent heat of vaporization of water vapor in the air is high. Therefore, the latent heat contribution rate of the total heat exchange of the indoor and outdoor air is much greater than the sensible heat contribution rate. Therefore, in order to improve the energy recovery rate of the total heat exchanger, to ensure fresh air in a closed space, and to improve the moisture and gas barrier properties of the total heat exchange membrane, it is an important research direction.
At present, the core component of the total heat exchange device, the total heat exchange membrane, is mostly made of commercial paper membrane, and the membrane has the following disadvantages: 1. the paper film is a full-permeable film which can not effectively block CO 2 Gas, while having poor mechanical properties; 2. the paper film is not flame-retardant, and is easy to mildew during use, thereby causing secondary pollution to air; 3. "trade-off" exists between moisture permeability and gas barrier properties. The composite polyamide total heat exchange membrane constructed by interfacial polymerization has boundary defects and gas leakage performance of different degrees. The former attempts to add nanoparticles such as montmorillonite, silica, ZIF-7 to the film and to improve the moisture permeability of the film by increasing the hydrophilicity of the film or by constructing selective "micro channels" in the film, however, due to the agglomeration of the nanoparticles, interfacial voids and gas leakage occur in the film, resulting in a decrease in the gas barrier properties of the film. In order to obtain the ultra-high gas barrier total heat exchange membrane, it is necessary to find a reasonable treatment method on the basis of ensuring the heat exchange efficiency.
Disclosure of Invention
In order to overcome the defects of the existing total heat exchange membrane, the invention provides a total heat exchange membrane doped with functional ZIF-7 nano particles and a preparation method thereof. The total heat exchange membrane consists of an ultrafiltration membrane supporting layer, a polyamide separation layer and functionalized ZIF-7 nano particles distributed in the polyamide layer. The preparation process comprises the following steps: adding the functionalized ZIF-7 nanoparticles into an oil phase, and forming a polyamide ultrathin separation layer added with the functionalized ZIF-7 nanoparticles by an interfacial polymerization method. The functionalized ZIF-7 nano particles can effectively regulate and control the interaction force of phase interfaces, avoid interface gaps, increase the compactness of the membrane, accurately construct a rapid transmission selective microscopic channel, and simultaneously increase the mechanical property and the flame retardant property of the membrane, increase the surface roughness of the membrane and increase the surface area of a separation layer, thereby improving the moisture permeability, the air resistance and the heat recovery efficiency. The total heat exchange membrane prepared by the invention has the characteristics of high moisture permeability, high gas resistance and high heat recovery efficiency, and the preparation method is simple and feasible, is easy to operate, can be suitable for the fields of air energy recovery, indoor air purification, fresh air systems and chemical industry environmental protection, and has good industrial application prospect.
The technical scheme of the invention is as follows:
a total heat exchange membrane doped with functional ZIF-7 nanoparticles, comprising: the composite membrane comprises an ultrafiltration membrane supporting layer, a polyamide separating layer and functionalized ZIF-7 nano particles distributed in the polyamide layer;
the ultrafiltration membrane supporting layer can be prepared from one or more of polysulfone, polyethersulfone, polyetherketone, polyarylsulfone, polyacrylonitrile and polyvinylidene fluoride;
the ultrafiltration membrane contains holes with the diameter of 1 nm-0.2 mu m, a small part of polyamide is positioned in the holes of the ultrafiltration membrane, and a large part of polyamide is positioned on the surface of one side of the ultrafiltration membrane.
The polyamide separation layer is prepared by interfacial polymerization of a water-phase amine monomer and an oil-phase acyl chloride monomer;
the functionalized ZIF-7 nano particles include but are not limited to ZIF-7-NH 2 、ZIF-7-OH、ZIF-7-CH 3 、ZIF-7-CH 2 OH、ZIF-7-C 2 H 5 、ZIF-7-C 3 H 7 One or more of the functionalized ZIF-7 nanoparticles; the particle size of the functionalized ZIF-7 nano particle is 20-500 nm.
A preparation method of a total heat exchange membrane doped with functional ZIF-7 nano particles comprises the following steps:
(1) Synthesis of functionalized ZIF-7 nanoparticles
Mixing a metal precursor solution and a ligand solution, stirring and reacting for 0.5-12 h at room temperature (20-30 ℃), then centrifugally collecting nanoscale solid particles, cleaning (using methanol), and drying in vacuum (50-120 ℃, 6-12 h) to obtain functionalized ZIF-7 nanoparticles;
the concentration of the metal precursor solution is 0.01-1 mol/L, the solvent is DMF (N, N-2 methyl formamide), and the metal precursor is selected from one or more of zinc oxide, zinc nitrate, zinc chloride, zinc sulfate, zinc acetate and the like;
the concentration of the ligand solution is 0.01-1 mol/L, the solvent is methanol, and the ligand is a mixture of benzimidazole and benzimidazole containing functional groups; the benzimidazole containing the functional group is selected from one or more of benzimidazoles such as 2-aminobenzimidazole, 2-hydroxybenzimidazole, 2-methylbenzimidazole, 2-hydroxymethylbenzimidazole, 2-ethylbenzimidazole, 2-propylbenzimidazole and the like;
the volume ratio of the metal precursor solution to the ligand solution is 1:1;
(2) Preparation of film-forming solution
Dissolving an amine monomer in deionized water at room temperature to prepare a water phase solution, dissolving an acyl chloride monomer in an organic solvent, adding the functionalized ZIF-7 nanoparticles obtained in the step (1), and performing ultrasonic dispersion uniformly to obtain an oil phase solution for later use;
in the aqueous phase solution, the mass fraction of amine monomers is 0.01-5% (preferably 1-3%), the amine monomers include but are not limited to one or more of piperazine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, ethylenediamine, hexamethylenediamine, 1,4-butanediamine, 4,4-diaminodiphenyl ether, 4,4, -diaminodiphenylmethane, o-biphenylmethylamine, 1,2-propanediamine, 1,3-propanediamine, 2,4-diaminotoluene, 1,2-cyclohexanediamine, 4,5-dichlorophthalenediamine, diethylenetriamine, pyromellitic triamine and derivatives thereof;
in the oil phase solution, the mass fraction of acyl chloride monomers is 0.01-5% (preferably 0.1-0.5%), the mass fraction of the functionalized ZIF-7 nanoparticles is 0.001-5% (preferably 0.03-1%), the mass fraction of the organic solvent is one or more selected from alkanes such as n-hexane, n-heptane, n-octane, n-dodecane, isododecane, isohexadecane and the like, and the acyl chloride monomers include but are not limited to one or more selected from isophthaloyl dichloride, terephthaloyl dichloride, phthaloyl dichloride, trimesoyl chloride, multi-aromatic sulfonyl chloride and derivatives thereof;
(3) Interfacial polymerization for preparing polyamide layer
At room temperature, firstly immersing an ultrafiltration membrane supporting layer in the water phase solution for 1-10 min (preferably 2-5 min), then taking out and removing the excessive water phase solution on the surface of the membrane, immersing the ultrafiltration membrane supporting layer in the oil phase solution for 20 s-10 min (preferably 30 s-2 min) to generate interfacial polymerization reaction, then taking out and airing in the air, and forming a polyamide layer added with functionalized ZIF-7 nano particles on the surface of the ultrafiltration membrane supporting layer;
(4) Post-treatment
And (3) carrying out heat treatment on the membrane at 50-90 ℃ (preferably 60-80 ℃) for 5-30 min (preferably 8-20 min) to obtain the total heat exchange membrane doped with the functional ZIF-7 nano particles.
The types of the total heat exchange membrane doped with the functional ZIF-7 nano particles comprise a flat membrane, a hollow fiber homogeneous membrane or a hollow composite membrane and a tubular membrane.
The invention has the beneficial effects that:
the functionalization of the ZIF-7 nano particles is realized by regulating and controlling the ligand structure of the ZIF-7 nano particles, and the functionalized ZIF-7 particles are successfully added in the interfacial polymerization process. The preparation method has the advantages that the functionalized ZIFs nanoparticles are doped in the polyamide separation layer, so that the interaction force of a phase interface can be effectively regulated and controlled, the interface gap is avoided, a rapid transmission selective micro channel is accurately constructed, the mechanical property of the membrane is increased, the surface roughness of the membrane is increased, the surface area of the separation layer is increased, and the moisture permeability, the air resistance and the heat recovery efficiency are improved.
The functionalized ZIF-7 nano-particles interact with a Polyamide (PA) film by forming hydrogen bonds or coordination bonds, so that the binding affinity is increased under the condition of not introducing serious defects, and the ZIFs nano-particles can be fixed in and on the polyamide layer to accurately construct a rapid transmission selective microscopic channel; meanwhile, the nano particles can be finely adjusted by surface functionalization and control of crystal size and morphology so as to achieve the purposes of high moisture permeability and high gas barrier property.
The prepared total heat exchange membrane has higher moisture permeability, air resistance and heat recovery performance than the total heat exchange membrane prepared by adding the non-functionalized ZIFs nanoparticles, and the preparation method is simple, feasible and easy to operate, and is suitable for the fields of air total heat recovery, air conditioning heating and ventilation energy recovery, indoor air purification, air dehumidification and heat and humidity recovery and chemical engineering environmental protection.
Drawings
FIG. 1 is a flow diagram of a process for preparing a total heat exchange membrane incorporating functionalized ZIF-7 nanoparticles.
FIG. 2 is an electron microscope photograph of (a) comparative example 1, (b) example 3, (c) example 5 and (d) the polyamide separation layer prepared in example 6;
FIG. 3 is an infrared image of ZIF-7 nanoparticles and functionalized ZIF-7 nanoparticles.
FIG. 4 is a graph showing performance tests of the blank total heat exchange membrane of comparative example 1, the total heat exchange membrane of comparative example 2 doped with non-functionalized ZIF-7 nanoparticles, and the total heat exchange membranes prepared in examples 1 to 6, wherein (a) is water vapor and CO 2 The transmission map and (b) the total heat exchange efficiency data map.
Detailed Description
The invention is further described below by means of specific examples, without the scope of protection of the invention being limited thereto.
The indoor environment for all total heat exchange membrane preparation in the examples is: the temperature is 25 ℃, the humidity is 45%, and the pressure is normal.
The polysulfone ultrafiltration membrane support layer used in the examples was purchased from the Hangzhou Water treatment center.
Example 1:
preparing a total heat exchange membrane doped with the functional ZIF-7 nano particles. The preparation method comprises the following specific steps:
(1) Adding 5mmol of Zn (NO) 3 ) 2 ·6H 2 Dissolving O in 50ml DMF to prepare Zn 2+ A solution; dissolving 5mmol of benzimidazole and 5mmol of 2-aminobenzimidazole in 50ml of methanol to prepare an imidazole solution; the imidazole solution was poured rapidly into Zn at room temperature 2+ Stirring the solution for 6 hours to obtainTo opalescent ZIF-7-NH 2 And (3) dispersing the mixture. High-speed centrifugal collection of the obtained nanoscale ZIF-7-NH 2 Washing the particles with methanol to obtain pure ZIF-7-NH 2 Vacuum drying at 120 deg.C for 12 hr to obtain solid powder ZIF-7-NH 2 ；
(2) Immersing the ultrafiltration membrane support layer in a 2wt% MPD (m-phenylenediamine) solution for 3min to form an aqueous phase liquid layer on the surface, taking out and air-drying the excess aqueous phase solution on the membrane surface, and immersing the ultrafiltration membrane support layer in 0.1wt% of each of TMC (trimesoyl chloride) and 0.05wt% of ZIF-7-NH 2 Carrying out interfacial polymerization reaction in the n-hexane solution for 1min, taking out, airing in the air, then carrying out heat treatment at 70 ℃ for 15min, and drying to obtain the total heat exchange membrane doped with the amino functionalized ZIF-7 nano material.
EXAMPLE 1 Perthermal exchange Membrane incorporating amino functionalized ZIF-7 nanoparticles prepared for Water vapor Permeability, CO 2 The permeability and enthalpy exchange efficiency are shown in figure 4, the water vapor permeability is 571.71GPU 2 The permeability is 16.72GPU, the wet exchange rate is 43.76 percent, the enthalpy exchange efficiency is 62.73 percent, and the heat exchange rate is 96.08 percent.
Example 2:
example 2 the rest was the same as in example 1 except that 5mmol of 2-aminobenzimidazole in step (1) of example 1 was changed to 5mmol of 2-hydroxybenzimidazole;
example 2A functionalized ZIF-7 nanomaterial modified Total Heat exchange Membrane having Water vapor Permeability, CO 2 The permeability and enthalpy exchange efficiency are shown in figure 4, the water vapor permeability is 580.24GPU 2 The permeability is 27.93GPU, the wet exchange is 44.83 percent, the enthalpy exchange efficiency is 63.51 percent, and the heat exchange rate is 96.91 percent.
Example 3:
example 3 the rest is the same as in example 1 except that 5mmol of benzimidazole in step (1) of example 1 is replaced with 5mmol of 2-methylbenzimidazole;
example 3A functionalized ZIF-7 nanomaterial modified Total Heat exchange Membrane having Water vapor Permeability, CO 2 The permeability and enthalpy exchange efficiency are shown in figure 4, the water vapor permeability is 614.61GPU 2 The permeability is 34.09GPU, the wet exchange is 45.59 percent, the enthalpy exchange efficiency is 63.03 percent, and the heat exchange rate is 96.88 percent.
Example 4:
example 4 the rest of the same procedure as in example 1 was repeated, except that 5mmol of benzimidazole in step (1) of example 1 was replaced with 5mmol of 2-hydroxymethylbenzimidazole;
example 4A functionalized ZIF-7 nanomaterial modified Total Heat exchange Membrane having Water vapor Permeability, CO 2 The permeability and enthalpy exchange efficiency are shown in figure 4, the water vapor permeability is 587.63GPU 2 The permeability is 21.46GPU, the wet exchange rate is 43.64 percent, the enthalpy exchange efficiency is 61.97 percent, and the heat exchange rate is 96.08 percent.
Example 5:
example 5 the rest of the same procedure as in example 1 was repeated, except that 5mmol of benzimidazole in step (1) of example 1 was changed to 5mmol of 2-ethylbenzimidazole;
example 5A functionalized ZIF-7 nanomaterial modified Total Heat exchange Membrane having Water vapor Permeability, CO 2 The permeability and enthalpy exchange efficiency are shown in figure 4, the water vapor permeability is 623.06GPU 2 The permeability is 27.86GPU, the wet exchange rate is 46.19 percent, the enthalpy exchange efficiency is 63.73 percent, and the heat exchange rate is 96.77 percent.
Example 6:
example 6 the rest is the same as in example 1 except that 5mmol of benzimidazole in step (1) of example 1 is replaced with 5mmol of 2-propylbenzimidazole;
example 6A functionalized ZIF-7 nanomaterial modified Total Heat exchange Membrane having Water vapor Permeability, CO 2 The permeability and enthalpy exchange efficiency are shown in figure 4, the water vapor permeability is 624.65GPU 2 The permeability is 20.42GPU, the wet exchange is 45.88%, the enthalpy exchange efficiency is 62.42%, and the heat exchange is 96.75%.
As shown in FIGS. 2 (b), (c) and (d), the polyamide separation layers obtained in examples 3, 5 and 6 showed that the functionalized ZIFs nanoparticles were clearly observed on the polyamide layer, and the particle diameter was 30 to 200nm.
Comparative example 1:
step (1): immersing the ultrafiltration membrane support layer in the 2wt% MPD solution for 3min to form an aqueous phase solution layer on the surface thereof, and removing the excess aqueous phase solution from the membrane surface;
step (2): and immersing the ultrafiltration membrane supporting layer in 0.1wt% TMC n-hexane solution for 1min to perform interfacial polymerization reaction, taking out, airing in the air, then performing heat treatment at 70 ℃ for 10min, and drying to obtain the blank total heat exchange membrane.
FIG. 2 (a) is an electron micrograph of the polyamide separation layer obtained in comparative example 1, in which only the polyamide layer containing no nanoparticles is visible.
Comparative example 1 preparation of total heat exchange membrane without ZIFs nanoparticles 2 The permeability and enthalpy exchange efficiency are shown in figure 4, the water vapor permeability is 586.07GPU 2 The permeability is 152.59GPU, the wet exchange is 40.35%, the enthalpy exchange efficiency is 60.83%, and the heat exchange is 95.15%.
Comparative example 2:
comparative example 2 the same procedure as in example 1 except for changing 5mmol of benzimidazole and 5mmol of 2-aminobenzimidazole to 10mmol of benzimidazole in step (1) of example 1;
comparative example 2 prepared total heat exchange membrane incorporating unfunctionalized ZIF-7 nanoparticles Water vapor Permeability, CO 2 The permeability and enthalpy exchange efficiency are shown in figure 4, the water vapor permeability is 589.05GPU 2 The permeability is 77.49GPU, the wet exchange is 42.76%, the enthalpy exchange efficiency is 61.91%, and the heat exchange is 95.99%.
CO of all examples and comparative examples 2 Permeability test conditions: testing at 25 ℃ by adopting a differential pressure method; enthalpy exchange efficiency test conditions: the fresh air temperature is 35 ℃ and the RH is 40 percent; the air exhaust temperature is 25 ℃, and the RH is 25%.
According to the total heat exchange membrane doped with the functionalized ZIF-7 nano particles, the functionalized ZIF-7 nano particles are added into an oil phase, and an interface polymerization method is used for forming the polyamide ultrathin skin layer doped with the functionalized ZIF-7 nano particles, so that high moisture permeability, high gas barrier and high heat recovery efficiency are ensured, and compared with a comparative example, the total heat exchange membrane not only has extremely low CO 2 Gas (es)Transmittance (10-40 GPU) and equivalent enthalpy exchange efficiency (60-65%). Meanwhile, the preparation method is simple and feasible, easy to operate and low in cost, and can be applied to the fields of air energy recovery, gas separation, indoor fresh air systems and chemical environmental protection.
The present invention is not limited to the above embodiments, and all embodiments are within the scope of the present invention as long as the requirements of the present invention are met.

Claims (10)

1. A total heat exchange membrane doped with functionalized ZIF-7 nano particles is characterized by comprising an ultrafiltration membrane supporting layer, a polyamide separation layer and functionalized ZIF-7 nano particles;
the polyamide separation layer is distributed on the surface and in the holes of the ultrafiltration membrane support layer;
the functionalized ZIF-7 nanoparticles are distributed in the polyamide separation layer.
2. The PEM incorporating the functionalized ZIF-7 nanoparticles of claim 1, wherein the ultrafiltration membrane support layer is made of one or more of polysulfone, polyethersulfone, polyetherketone, polyarylsulfone, polyacrylonitrile, and polyvinylidene fluoride.
3. The pem of claim 1 incorporating functionalized ZIF-7 nanoparticles wherein said functionalized ZIF-7 nanoparticles comprise ZIF-7-NH 2 、ZIF-7-OH、ZIF-7-CH 3 、ZIF-7-CH 2 OH、ZIF-7-C 2 H 5 、ZIF-7-C 3 H 7 One or more of them, the particle size is 20-500 nm.
4. The enthalpy exchange membrane doped with functionalized ZIF-7 nanoparticles, according to claim 1, wherein the type of the enthalpy exchange membrane is a flat sheet membrane, a hollow fiber homogeneous membrane, or a hollow composite membrane and a tubular membrane.
5. The method of preparing a total heat exchange membrane incorporating functionalized ZIF-7 nanoparticles as claimed in claim 1, comprising the steps of:
(1) Synthesis of functionalized ZIF-7 nanoparticles
Mixing a metal precursor solution and a ligand solution, stirring and reacting at room temperature, then centrifugally collecting nano-scale solid particles, cleaning with methanol, and drying in vacuum to obtain functionalized ZIF-7 nanoparticles;
(2) Preparation of film-forming solution
Dissolving amine monomers in deionized water at room temperature to prepare a water phase solution, dissolving acyl chloride monomers in an organic solvent, adding the functionalized ZIF-7 nanoparticles obtained in the step (1), and uniformly dispersing by ultrasonic to obtain an oil phase solution for later use;
(3) Preparation of polyamide layer by interfacial polymerization
Immersing an ultrafiltration membrane supporting layer in an aqueous phase solution for 1-10 min at room temperature, taking out, removing the excessive aqueous phase solution on the surface of the membrane, immersing the ultrafiltration membrane supporting layer in an oil phase solution for 20 s-10 min to generate an interfacial polymerization reaction, taking out, airing in the air, and forming a polyamide layer containing functionalized ZIF-7 nano particles on the surface of the ultrafiltration membrane supporting layer to obtain a composite membrane;
(4) Post-treatment
And (4) carrying out heat treatment on the composite membrane obtained in the step (3) at 50-90 ℃ for 5-30 min to obtain the full heat exchange membrane doped with the functional ZIF-7 nano particles.
6. The method of preparing a total heat exchange membrane incorporating functionalized ZIF-7 nanoparticles, according to claim 5, wherein in step (1), the volume ratio of the metal precursor solution to the ligand solution is 1:1, stirring for 0.5 to 12 hours at the temperature of between 20 and 30 ℃ under the condition of stirring reaction; the vacuum drying conditions were: drying for 6-12 h at 50-120 ℃.
7. The method of preparing the enthalpy exchange membrane doped with the functionalized ZIF-7 nanoparticles according to claim 5, wherein in the step (1):
the concentration of the metal precursor solution is 0.01-1 mol/L, the solvent is N, N-2 methyl formamide DMF, and the metal precursor is selected from one or more of zinc oxide, zinc nitrate, zinc chloride, zinc sulfate and zinc acetate;
the concentration of the ligand solution is 0.01-1 mol/L, the solvent is methanol, the ligand is a mixture of benzimidazole and benzimidazole containing functional groups, and the benzimidazole containing the functional groups is selected from one or more of 2-aminobenzimidazole, 2-hydroxybenzimidazole, 2-methylbenzimidazole, 2-hydroxymethylbenzimidazole, 2-ethylbenzimidazole and 2-propylbenzimidazole.
8. The method of preparing a total heat exchange membrane doped with functionalized ZIF-7 nanoparticles as claimed in claim 5, wherein in the step (2):
in the aqueous phase solution, the mass fraction of amine monomers is 0.01-5%, the amine monomers comprise but are not limited to one or more of piperazine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, ethylenediamine, hexanediamine, 1,4-butanediamine, 4,4-diaminodiphenyl ether, 4,4, -diaminodiphenylmethane, o-biphenylmethylamine, 1,2-propanediamine, 1,3-propanediamine, 2,4-diaminotoluene, 1,2-cyclohexanediamine, 4,5-dichloroo-phenylenediamine, diethylenetriamine and pyromellitic triamine;
in the oil phase solution, the mass fraction of acyl chloride monomer is 0.01-5%, the mass fraction of functionalized ZIF-7 nano particles is 0.001-5%, the organic solvent is selected from one or more of n-hexane, n-heptane, n-octane, n-dodecane, isododecane and isohexadecane, and the acyl chloride monomer comprises one or more of isophthaloyl dichloride, terephthaloyl dichloride, phthaloyl dichloride, trimesoyl chloride and multi-element aromatic sulfonyl chloride.
9. The method of preparing the enthalpy-exchange membrane doped with the functionalized ZIF-7 nanoparticles, according to claim 5, wherein in the step (3), the ultrafiltration membrane support layer is immersed in the aqueous phase solution for 2 to 5min and immersed in the oil phase solution for 30s to 2min.
10. The method of preparing a total heat exchange membrane doped with functionalized ZIF-7 nanoparticles, according to claim 5, wherein the post-treatment temperature in the step (4) is 60 to 80 ℃ and the time is 8 to 20min.
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CN104209021A (en) * 2014-09-03 2014-12-17 北京林业大学 Preparation method of aromatic polyamide film modified by ZIF-8 type metal-organic framework material
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