CN114471200A - Method for improving preparation of Zr-based MOF film through intermediate modification layer and forward osmosis application of method - Google Patents
Method for improving preparation of Zr-based MOF film through intermediate modification layer and forward osmosis application of method Download PDFInfo
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Abstract
A method for improving preparation of a Zr-based MOF membrane by using an intermediate modification layer and forward osmosis application thereof belong to the technical field of environmental membrane separation. The introduction of the nano composite titanium dioxide intermediate layer improves the surface property of the support layer, provides good growth conditions for interfacial polymerization, and simultaneously introduces novel porous nano materials MOF-801 and UiO-66 to grow a more compact polyamide layer, the porous MOF-801 and UiO-66 materials provide an additional low-resistance transmission channel for the transmission of water and solvent molecules, so that the water flux and the organic solvent flux are improved, and meanwhile, the proper pore diameters of the polyamide membrane, the MOF-801 and the UiO-66 effectively block the passage of salt ions, so that the reverse salt flux is reduced, and the balance problem of membrane permeability and selectivity can be effectively solved. In order to further improve the permeability and stability of the membrane, pure UO-66 membranes (Defect-free-UO-66 and ML-UO-66) are developed and used in the forward osmosis process, and remarkable effect is achieved. Provides a new idea and a new method for the structural design of the active layer of the forward osmosis membrane.
Description
Technical Field
The invention relates to a preparation technology of a ceramic-based TFN forward osmosis membrane, provides a method for preparing a defect-free ceramic-based TFN forward osmosis membrane by modifying a ceramic substrate with a titanium dioxide intermediate layer and introducing novel materials MOF-801 and UiO-66, and simultaneously adopts gamma-Al2O3The pure UiO-66 membrane of the modification layer develops the application of the new forward osmosis field, which belongs to the technical field of environmental membrane separation.
Background
The membrane separation technology has the advantages of low energy consumption, high efficiency, environmental friendliness and the like, so that the membrane separation technology is very widely concerned and has important application prospects in the aspects of solving the problems of environment and energy. Forward osmosis technology has received much attention because of its advantages such as low cost, low pollution and high water recovery.
As the core forward osmosis membrane of forward osmosis technology (FO), which is now mainly based on TFC membranes (thin film composite membranes), the membrane permeability-selectivity tradeoff and the long-term stability of the support are some of the challenges faced by forward osmosis technology. The forward osmosis membrane reported in the literature at present mainly comprises an organic carrier, and compared with the organic carrier, the inorganic carrier has the advantages of high mechanical strength, strong thermal stability and chemical stability and the like, but the traditional ceramic carrier has higher cost. The mullite ceramic support body prepared by adopting the industrial solid waste fly ash and the low-cost bauxite as raw materials not only reduces the cost of the ceramic support body, but also increases the recycling value of the industrial solid waste and reduces the environmental hazard of the industrial solid waste.
It is very easy to prepare polyamide membranes directly on organic carriers because of the small surface pore size and low roughness of organic carriers; the pore diameter and the roughness of the surface of the mullite ceramic carrier are larger, so that a polyamide layer grows in the pores, the grown polyamide layer has defects, the thickness of an effective film is increased, the resistance encountered during water transmission is increased, the water flux is smaller, and the reverse salt flux is larger. This is detrimental to forward osmosis applications.
The pure UiO-66 membrane is widely applied due to the advantages of high stability, adjustable pore diameter and the like, and mainly relates to the following components: pervaporation process, reverse osmosis process. At present, no research is carried out on a pure UiO-66 membrane forward osmosis process, and the main challenges are that the reverse salt flux is too high due to poor compactness of the prepared membrane, the water flux is low due to the fact that the pore size cannot be adjusted, and the like.
Disclosure of Invention
The invention aims to provide a titanium dioxide interlayer modified ceramic substrate, a method for preparing a defect-free ceramic-based TFN forward osmosis membrane and application thereof. By introducing a titanium dioxide intermediate layer and novel materials MOF-801 and UiO-66, a compact TFN forward osmosis membrane grows on a ceramic carrier, and meanwhile, a pure UiO-66 membrane is applied to the forward osmosis process, so that the prepared membrane has a wide prospect in the fields of seawater desalination, food processing and organic solvent recovery.
The technical scheme of the invention is as follows:
the method for preparing the defect-free ceramic-based TFN forward osmosis membrane by introducing a novel material MOF-801 comprises the following steps:
(1) preparation of mullite ceramic carrier
The method comprises the steps of taking industrial solid waste fly ash and bauxite as raw materials, preparing a mullite green body by a wet spinning-phase conversion method, and calcining at high temperature to obtain the mullite ceramic carrier.
(2) Preparation of titanium dioxide intermediate layer
(2.1) putting the mullite ceramic carrier with the aperture of 600-800 nm into an ethanol solution for washing for 30-60min, then washing the mullite ceramic carrier clean by deionized water, and putting the mullite ceramic carrier into an oven for drying.
(2.2) preparing an inorganic transition layer on the ceramic hollow fiber substrate: firstly, preparing titanium dioxide suspension with the concentration of 10-20 wt%, and uniformly coating the outer surface of the ceramic hollow fiber substrate by using a dip-coating process; in the process, the dipping time is controlled to be 5-10 s, the pulling speed is controlled to be 0.5-1.5 cm/s, the successfully dipped carrier is obtained, then the carrier is placed in a constant-temperature humidity drying box to be dried for more than 12 h, and is roasted for 10-12 h at the temperature of 500-900 ℃ in a high-temperature furnace with the sintering atmosphere being air, and the titanium dioxide transition layer with the thickness of 3.0-5.0 mu m is prepared on the ceramic hollow fiber substrate.
(3) Synthesis of MOF-801 powder
Fumaric acid (0.081 g, 3.5 mmol) and ZrOCl2·8H2Dissolving O (0.23 g, 0.70 mmol) in a DMF/formic acid (35 mL/5.3 mL) mixture solvent, stirring for 10-30 min by an electromagnetic stirrer until a solute is dissolved, and then putting the solution into a reaction kettle to react for 24 h in an oven at 100-150 ℃. And after the reaction is finished, centrifuging the solution after the reaction for 5-10 min at the rotating speed of 6000-10000 rpm to obtain white precipitate. And washing the white precipitate with N-N dimethylformamide for 48-72 h, 2-4 times per day, and exchanging with anhydrous methanol for 48-72 h, 2-4 times per day. And finally, placing the white precipitate in a vacuum drying oven for activation for 24-48 h at 100-180 ℃ to obtain usable MOF-801, and storing the usable MOF-801 in a sealed manner to prevent the MOF-801 from absorbing moisture in the air.
(4) Synthesis of ceramic-based TFN forward osmosis membrane
Preparing a defect-free forward osmosis membrane on a ceramic substrate modified by a titanium dioxide transition layer, putting 0.02-0.1 wt% MOF-801 into 0.1-0.4 wt% TMC solution, performing ultrasound for 30-60min, and preparing 2-5 wt% MPD solution. The ceramic substrate modified by the titanium dioxide middle layer is placed in an MPD solution for 3-10 min, then dried at room temperature for 5-10 min, reacted in a TMC solution for 1-3 min, and finally the sample is placed in a 60-90 ℃ oven for 5-10 min for further reaction to prepare the defect-free ceramic-based TFN forward osmosis membrane.
(5) Evaluation of ceramic-based TFN Forward osmosis Membrane integrity
To assess the integrity of ceramic-based TFN forward osmosis membrane composite membranes, the salt rejection (Rs) of the membranes was determined using a cross-flow reverse osmosis unit. And testing the selectivity of the membrane under the transmembrane pressure of 3-6 bar. And pre-pressing for 30-60min before starting measurement to ensure the stability of the measured value. Water permeability is obtained by measuring the water flux through the membrane. The rejection is measured using a sodium chloride solution with a concentration of 200 ppm. RsAs retention rate, CfAnd CpThe concentrations of the permeate and the feed are respectively (mol/L).
(6) Application of ceramic-based TFN forward osmosis membrane
The application of the ceramic-based TFN forward osmosis membrane is that the defect-free ceramic-based TFN forward osmosis membrane is put into a hollow fiber membrane module to be used for water treatment. In the ceramic-based TFN forward osmosis membrane, the aperture of the polyamide membrane, the MOF-801 powder and the UiO-66 powder is larger than the kinetic diameter of water, and meanwhile, the hydrophilic Zr-MOF has excellent water absorption capacity and proper aperture, so that an extra low-resistance water transmission channel can be provided for water molecules, and salt ions can be effectively intercepted, thereby improving the membrane performance and being used for seawater desalination. Also, in terms of organic solvent recovery, the pore diameter of the polyamide membrane and MOF-801 and UiO-66 powder is larger than the hydrated ionic radius of ethanol and smaller than the hydrated ionic radius of monovalent salt ions, and the mullite carrier, the polyamide membrane and the MOF-801 powder are very stable in ethanol solvent, so that the polyamide membrane and the MOF-801 powder can be used for organic solvent forward osmosis application.
(II) a method for preparing UiO-66 doped ceramic-based TFN forward osmosis membrane comprises the following steps:
s1, preparation of mullite ceramic carrier
Dissolving polyether sulfone and additive polyvinylpyrrolidone in N-methyl pyrrolidone, wherein the mass ratio of polyether sulfone: polyvinylpyrrolidone: n-methyl pyrrolidone =1:0.1-0.2:4-6, and ball milling is carried out to completely dissolve the N-methyl pyrrolidone so as to prepare polymer slurry;
then adding the fly ash and bauxite with the material ratio of 0.85:1 into the polymer slurry to obtain casting mold slurry with the solid content of 40-55 wt%, and continuously ball-milling for more than 48 h to ensure uniform dispersion; vacuumizing the casting film slurry for 2 h to remove residual bubbles, pouring the casting film slurry into a slurry tank, applying nitrogen pressure to the slurry tank by using deionized water as an inner core liquid, immersing a fiber wet film extruded from a spinning nozzle into deionized water of an external solidification bath through an air gap of 15-30 cm, and gelling and curing for 24 h to form a hollow fiber film green body; sintering at 1200 ℃ and 1400 ℃ to obtain the mullite ceramic carrier;
s2. preparation of titanium dioxide interlayer
Putting the mullite ceramic carrier with the aperture of 400-700 nm into an ethanol solution for washing for 30-60min, then washing the mullite ceramic carrier clean by deionized water, and putting the mullite ceramic carrier into an oven for drying;
preparing an inorganic transition layer on a ceramic hollow fiber substrate: firstly, preparing titanium dioxide suspension with the concentration of 10-20 wt%, and uniformly coating the outer surface of the ceramic hollow fiber substrate by using a dip-coating process; in the process, the dipping time is controlled to be 5-10 s, the pulling speed is controlled to be 0.5-1.5 cm/s, and the carrier is placed in a constant-temperature humidity drying box for drying for more than 12 h after being dipped; roasting for 10-12 hours at the temperature of 500-900 ℃ in a high-temperature furnace with air as a sintering atmosphere, and preparing a titanium dioxide transition layer with the thickness of 3.0-5.0 mu m on a ceramic hollow fiber substrate;
s3 Synthesis of UiO-66 powder
Mixing terephthalic acid and ZrCl4Dissolving in a mixed solvent of N-N dimethylformamide and acetic acid, stirring for 10-30 min by using an electromagnetic stirrer until the mixed solvent is dissolved, and reacting for 24 h at 120-220 ℃; after the reaction is finished, centrifuging the solution after the reaction for 5-10 min at the rotating speed of 6000-10000 rpm to obtain white precipitate; washing the white precipitate with N-N dimethylformamide for 48-72 h, and then exchanging with anhydrous methanol for 48-72 h; finally, the white precipitate is put in the vacuumActivating for 24-48 h in an air drying oven at the temperature of 100-180 ℃ to obtain UiO-66; the terephthalic acid: ZrCl4The molar ratio of N-N dimethylformamide to acetic acid in the mixed solvent is 1:1-5, and the volume ratio of N-N dimethylformamide to acetic acid in the mixed solvent is 10-2: 1;
s4, synthesis of ceramic-based TFN forward osmosis membrane
Putting 0.02-0.1 wt% of UiO-66 into 0.1-0.4 wt% of trimesoyl chloride solution, performing ultrasonic treatment for 30-60min, and preparing 2-5 wt% of m-phenylenediamine solution; the ceramic substrate modified by the titanium dioxide middle layer is placed in m-phenylenediamine solution for 3-10 min, then dried for 5-10 min at room temperature, reacted in trimesoyl chloride solution for 1-3 min, and finally the sample is placed in a 60-90 ℃ oven for 5-10 min for further reaction to prepare the UiO-66 doped ceramic-based TFN forward osmosis membrane.
(III) Gamma-Al2O3The method for preparing the ceramic-based pure Defect-free-UiO-66 forward osmosis membrane by modifying the ceramic substrate with the middle layer comprises the following steps:
(1) preparation of zirconia ceramic carrier
The zirconia ceramic carrier is prepared by taking industrial zirconia powder with the particle size of 200nm as a raw material, preparing a zirconia green body by a wet spinning-phase conversion method, and calcining at high temperature.
（2）γ-Al2O3Preparation of the intermediate layer
Preparing gamma-Al oxide with concentration of-0.05-0.2 wt%2O3Sol, coating uniform gamma-Al on the outer surface of the zirconia hollow fiber substrate by using a dipping process2O3Sol; in the process, the dipping time is controlled to be 1 s, the pulling speed is controlled to be 0.5 cm/s to obtain a uniformly coated pre-carrier, then the carrier is placed in a constant temperature and humidity drying box to be dried for more than 72 h, and is roasted for 2 h in a high-temperature furnace with air as sintering atmosphere at the temperature of 750 ℃, and the gamma-Al with the thickness of 1.0 mu m is prepared on a zirconia hollow fiber substrate2O3Transition layer, final preparation of ZrO2@γ-Al2O3A substrate.
(3) Preparation of pure Defect-free-UiO-66 film
At ZrO2@γ-Al2O3Preparing an ultrathin ML-UiO-66 film on a substrate: ZrO with both ends sealed by unsintered tape2@γ-Al2O3The substrate is vertically arranged in a polytetrafluoroethylene reaction kettle according to ZrCl4：H2BDC: DMF ═ 1-5: 1-5: preparing a synthetic mother solution of the UiO-66 film according to the molar ratio of 500-600, uniformly stirring, and then carrying out in-situ crystallization for 16h at the temperature of 220 ℃ to prepare the complete and continuous metal organic framework Defect-free-UiO-66 film with crystal internal defects.
(tetra) gamma-Al2O3The method for preparing the ceramic-based pure ML-UiO-66 forward osmosis membrane by modifying the ceramic substrate by the intermediate layer comprises the following steps:
(1) preparation of pure ML-UiO-66 film
ZrO prepared in the third section2@γ-Al2O3Preparing an ultrathin ML-UiO-66 film on a substrate: ZrO with both ends sealed by unsintered tape2@γ-Al2O3The substrate is vertically arranged in a polytetrafluoroethylene reaction kettle according to ZrCl4：H2BDC：CH3COOH: DMF ═ 1-5: 1-5: 20-50: preparing a synthetic mother solution of the ML-UiO-66 film according to the molar ratio of 500-600, uniformly stirring, and then carrying out in-situ crystallization for 48 h at the temperature of 120 ℃ to prepare the complete and continuous ML-UiO-66 (ML: Msing-linker) film with the metal organic framework and the internal defects of the crystal.
(2) Application of pure UiO-66 forward osmosis membrane
The Defect-free-UiO-66 membrane and the ML-UiO-66 (ML: Msing-linker) membrane are collectively called as pure UiO-66 membrane, and the complete pure UiO-66 membrane is put into a hollow fiber membrane module for water treatment. The aperture of the pure UiO-66 membrane is larger than the dynamic diameter of water, and meanwhile, the hydrophilic pure UiO-66 membrane has good hydrophilicity, so that a low-resistance water transmission channel can be provided for water molecules, and simultaneously, hydrated ions of salt can be effectively intercepted, so that the pure UiO-66 membrane can be used for the forward osmosis process. In addition, the stable coordination capacity of the Zr clusters in the pure UiO-66 membrane ensures the stable operation of the pure UiO-66 membrane in acidic, alkaline and high-chlorine water environments, so that the pure UiO-66 membrane can be directly used for real wastewater treatment.
The invention has the beneficial effects that:
to produce defect-free polyamide membranes on inorganic ceramic supports, TiO was introduced2The middle layer enables the macropores on the surface of the mullite carrier to be covered, so that uniform micropores and a smoother surface are formed, and the polyamide layer is only formed on TiO2The surface of the middle layer grows to generate a polyamide layer with thinner thickness, and the increase of the crosslinking degree also means that the film is denser. However, the water flux is affected, and optimization of the membrane performance is required.
In order to further improve the film performance, the MOFs has good compatibility with the polyamide film, and the MOFs has inorganic and organic characteristics, so that relatively ideal interface gaps can be formed between the MOFs and the polyamide film, and the selectivity of the film is not sacrificed. In addition, Metal Organic Frameworks (MOFs) as a novel porous material have the advantages of high porosity, proper pores, specific surface area and the like. Because the hydrophilic MOF-801 has superior water absorption capacity and proper pore diameter, an additional low-resistance water transmission channel can be provided for water molecules, salt ions can be effectively intercepted, the balance problem of membrane permeability and selectivity can be effectively overcome, and meanwhile, the mullite ceramic carrier has the advantages of high mechanical strength, strong thermal stability and chemical stability and the like, and the problem of long-term stability is effectively solved. The prepared defect-free ceramic-based forward osmosis membrane has a good application prospect in the fields of seawater desalination and organic solvent forward osmosis:
(1) an inorganic ceramic support was used as TFN forward osmosis membrane support. Compared with the existing organic carrier, the mullite ceramic carrier has the advantages of high hydrophilicity, high porosity, high mechanical strength, good pollution resistance, chemical and thermal stability and the like, and provides a new carrier for preparing the high-performance forward osmosis membrane.
(2) The nano composite titanium dioxide intermediate layer is introduced, the surface property of the supporting layer is changed, good growth conditions are provided for interfacial polymerization, a novel porous nano material MOF-801 is introduced, a more compact PA layer grows, an extra low-resistance transmission channel is provided for water transmission by the porous MOF-801 material, and salt ions are effectively prevented from passing through by the appropriate pore size, so that reverse salt flux is reduced, and a new thought and a new method are provided for improving the structure and the performance of the active layer.
(3) Compared with the TFN film doped with Zr-MOFs, the pure UiO-66 film has better transmission performance and stability. The introduction of ligand deletion in the pure UiO-66 membrane crystal and the research of forward osmosis process widen the application range of forward osmosis technology, and particularly can be better applied to acid-base and high-chlorine water environments. Provides a new scheme for the design and preparation of the next generation forward osmosis membrane.
Drawings
FIG. 1 is an electron microscope image of a mullite ceramic carrier.
FIG. 2 is a pore size and roughness characterization of a mullite ceramic support.
FIG. 3 is an electron microscope image of a mullite-titania composite film.
Fig. 4 is a pore size and roughness characterization of the mullite-titania composite membrane.
FIG. 5 is an electron micrograph of a ceramic based TFN forward osmosis membrane.
FIG. 6 is a graph of the performance of a ceramic based TFN forward osmosis membrane for seawater desalination treatment.
Fig. 7 is a ceramic based TFN forward osmosis membrane regenerability study.
FIG. 8 is a graph of forward osmosis performance of ceramic based Defect-free-UiO-66 membranes.
FIG. 9 is a graph of the forward permeability of a ceramic based ML-UiO-66 membrane.
FIG. 10 is a graph of the acid and alkali stability of a ceramic based ML-UiO-66 film.
FIG. 11 is a graph of real petrochemical wastewater treatment performance of ceramic-based ML-UiO-66 membranes.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
1. Preparation of mullite carrier:
the mullite green body is prepared by taking fly ash and bauxite as raw materials through a wet spinning-phase conversion method. First, 16 g of PES and 2 g of PVP as an additive were dissolved in 64 g of NMP, and the mixture was ball-milled for 6 hours to completely dissolve the PES and the additive, thereby preparing a polymer slurry. Then 46 g of fly ash and 54 g of bauxite are added into the polymer solution, and ball milling is continuously carried out for more than 48 h, so that uniform ball milling is ensured. The prepared casting film slurry is firstly vacuumized for 2 hours until the residual bubbles are removed. And then pouring the hollow fiber membrane into a slurry tank, wherein the inner core liquid is deionized water, the flow rate is 30 mL/min, applying 0.1 MPa nitrogen pressure, immersing the fiber wet membrane extruded from a spinning nozzle into the deionized water of an external coagulation bath through an air gap of 15 cm, and gelling and curing for 24 h to obtain a hollow fiber membrane green body. And sintering at 1250 ℃, and characterizing the appearance, the pore diameter and the roughness of the obtained mullite sample, wherein the pore diameter of the surface of the carrier is larger, the average pore diameter is about 550 nm, and the roughness is Ra =169 nm, so that a defective polyamide film is easily generated, as shown in figure 1 and figure 2.
2. Preparation of mullite-titanium dioxide composite film
20 weight percent of anatase type nano TiO2Powder, 5.0wt% of dispersant polyacrylic acid (PAA, Mw = 5000), 5.0wt% of stabilizer polyacrylic acid (PAA, Mw = 20000) and deionized water are put into a polyurethane ball milling tank together, and the mixture is ball milled for 48 h to be uniformly mixed. Then ammonia water is used for adjusting the PH value of the mixed solution to 9.5, and finally the stably dispersed nano TiO is obtained2And (3) suspension.
Uniformly coating the outer surface of the ceramic hollow fiber substrate by using a dip-coating process; in the process, the dipping time is controlled to be 5 s, the lifting speed is controlled to be 1 cm/s, the successfully dipped carrier is obtained, then the carrier is placed in a constant-temperature humidity drying box to be dried for more than 12 h, the carrier is roasted for 12 h at the temperature of 800 ℃ in a high-temperature furnace with the air sintering atmosphere, and the titanium dioxide transition layer with the thickness of 5.0 mu m is prepared on the ceramic hollow fiber substrate. The appearance, the pore diameter and the roughness of the obtained mullite-titanium dioxide composite membrane sample are characterized, as shown in fig. 3 and fig. 4, the surface pore diameter is larger, the average pore diameter is about 300 nm, and the roughness is Ra =31 nm, which shows that the pore diameter and the roughness are reduced by the existence of titanium dioxide, and the compact polyamide membrane is favorably formed.
Preparation of MOF-801 powder
0.401 g of fumaric acid and 0.23g of zirconium oxychloride were dissolved in 35ml of N-N dimethylformamide and 3.5 ml of formic acid solution, stirred by an electromagnetic stirrer until the solute was dissolved, and then placed in a reaction vessel to react for 24 hours in an oven at 120 ℃. After the reaction is finished, the solution after the reaction is centrifuged for 5 min at the rotating speed of 8000 rpm, and white precipitate is obtained. The white precipitate was washed with N-N dimethylformamide for 72 h, 3 times daily, and then exchanged with anhydrous methanol for 72 h, 3 times daily. And finally, putting the white precipitate into a vacuum drying oven to be activated for 24 h under the condition of 150 ℃ to obtain usable MOF-801, and storing the usable MOF-801 in a sealing manner to prevent the usable MOF-801 from absorbing moisture in the air.
4. Preparation of ceramic-based TFN forward osmosis membrane
The preparation of the ceramic-based TFN membrane is realized by introducing a new MOF-801 material, and because the MOF-801 material is unstable in alkaline conditions (the PH of m-phenylenediamine dissolved in water is 9-10), the MOF-801 with the concentration gradient of 0.04 wt% -0.12 wt% is put into n-hexane solution for ultrasonic treatment, so that the MOF-801 is uniformly dispersed. Then, in the same process as the preparation of the TFC membrane, the mullite-titanium dioxide composite membrane is firstly soaked in m-phenylenediamine solution for 3min, then dried in the air until no water drop is visible to the naked eye, and then soaked in TMC solution containing MOF-801 for interfacial polymerization for 1 min. The prepared film was placed in an oven for a subsequent heat treatment at 60 ℃ (5 min). The prepared film is stored in deionized water, an electron microscope image of the film is shown in figure 5, the surface of the TFN film has the ridge-valley polyamide morphology and also has regular octahedral MOF-801, and the successful preparation of the ceramic-based TFN film is proved.
Evaluation of integrity of 5 ceramic based TFN Forward osmosis membranes
The salt rejection (Rs) of the membranes was measured using a cross-flow reverse osmosis unit. The membranes were tested for permeability and selectivity at a transmembrane pressure of 5 bar. Prepressing for 60min before starting measurement to ensure the stability of the measured value. From the test results, the retention rate of the ceramic-based TFN forward osmosis membrane reaches 95%, which indicates that the forward osmosis membrane is complete, compact and free of defects.
6. Application effect of ceramic-based TFN forward osmosis membrane for seawater desalination
The work firstly uses porous ceramic mullite as a substrate, and provides a titanium dioxide transition layer modification strategy to prepare the defect-free ceramic-based TFN forward osmosis membrane. The synthesized ceramic-based TFN forward osmosis membrane is used for seawater desalination, and the specific experiment is as follows: and (3) carrying out performance test on the prepared membrane by using deionized water as a raw material solution and 1M NaCl as a drawing solution.
From FIG. 6, it can be seen that the water flux in FO mode of directly preparing the forward osmosis membrane on the mullite carrier is 6.9 + -1.2L/m2h, reverse salt flux of 10. + -. 0.7 g/m2h, the defect of the forward osmosis membrane directly prepared on the mullite carrier is shown, so that salt ions pass through the forward osmosis membrane.
The water flux of the forward osmosis membrane prepared on the titanium dioxide modified carrier in the FO mode is 13.74 +/-0.9L/m2h, reverse salt flux of 5.2. + -. 0.5 g/m2And h, compared with the forward osmosis membrane directly prepared on the mullite carrier, the water flux is improved, and the reverse salt flux is reduced, which shows that compared with the forward osmosis membrane directly prepared on the carrier, the forward osmosis membrane prepared on the carrier modified by titanium dioxide is more compact and thinner.
On a titanium dioxide modified carrier, a novel material MOF-801 is introduced to prepare a TFN forward osmosis membrane, and the water flux of the TFN forward osmosis membrane in an FO mode is 22 +/-0.9L/m2h, reverse salt flux of 3.9. + -. 0.5 g/m2h. Compared with the former two, the ceramic-based TFN forward osmosis membrane has improved water flux and reverse salt flux, which shows that the ceramic-based TFN forward osmosis membrane is complete and has no defects, and the MOF-801 provides an additional low-resistance water transmission channel for water molecules, and meanwhile, salt ions are effectively intercepted, so that the ceramic-based TFN forward osmosis membrane has a good effect in seawater desalination application.
In order to further study the anti-pollution performance of the ceramic-based TFN forward osmosis membrane in actual seawater, an anti-pollution test was carried out by using 250 mg/L of sodium alginate as a model pollutant. As can be seen from fig. 7, the flux of the ceramic-based TFN forward osmosis membrane after stable operation is higher than the flux of the ceramic-based TFC forward osmosis membrane, which indicates that the anti-pollution performance of the ceramic-based TFN forward osmosis membrane is better to a certain extent, and a more hydrophilic membrane surface is easier to form a water layer to block the hydrophobic attachment of sodium alginate. After washing, the water flux of the ceramic-based TFC forward osmosis membrane can be recovered to about 75% of the original flux, and the water flux of the ceramic-based TFN forward osmosis membrane can be recovered to about 90%, which indicates that the pollution of the ceramic-based TFN forward osmosis membrane can achieve a better result through physical cleaning to a certain extent, namely the pollution is reversible.
7. Application effect of ceramic-based TFN forward osmosis membrane in forward osmosis of organic solvent
Because the pore diameter (about 0.5 nm) of the polyamide membrane or the pore diameter (average 0.6 nm) of the MOF-801 powder is larger than the kinetic diameter (0.44 nm) of ethanol molecules and smaller than the hydrated ion diameters of univalent lithium ions (0.76 nm) and chloride ions (0.66 nm), and meanwhile, the mullite carrier, the polyamide membrane and the MOF-801 powder are very stable in an ethanol solvent, the prepared ceramic-based TFN forward osmosis membrane can be used for forward osmosis application of an organic solvent. In the experimental process, ethanol is used as a raw material solution, 2M lithium chloride dissolved in ethanol is used as a drawing solution, and experimental results show that the ethanol flux of the ceramic-based TFN forward osmosis membrane reaches 3.5 +/-0.3L/M in an AL-FS mode2h, reverse salt flux of 0.8 + -0.2 g/m2h, the retention rate of the enrofloxacin can reach 99.7%, which shows that the ceramic-based TFN forward osmosis membrane has good effect in the application of forward osmosis of organic solvent.
For other organic solvents, the ceramic-based TFN forward osmosis membrane also has higher solvent flux. Taking the organic solvent methanol as an example, the kinetic diameter (0.38 nm) of the molecule is also smaller than the pore diameter of the polyamide membrane and the MOF-801 powder. The methanol flux of the ceramic-based TFN forward osmosis membrane reaches 10.5 +/-0.6L/m in an AL-FS mode2h, reverse salt flux of 1.6. + -. 0.17 g/m2 h。
Example 2
1.γ-Al2O3The method for preparing the ceramic-based pure Defect-free-UiO-66 forward osmosis membrane by modifying the ceramic substrate with the middle layer comprises the following steps:
(1) preparation of zirconia ceramic carrier
The zirconia ceramic carrier is prepared by taking industrial zirconia powder with the particle size of 200nm as a raw material, preparing a zirconia green body by a wet spinning-phase conversion method, and calcining at high temperature.
（2）γ-Al2O3Preparation of the intermediate layer
Preparing 0.1wt% oxide gamma-Al2O3Sol, coating uniform gamma-Al on the outer surface of the zirconia hollow fiber substrate by using a dipping process2O3Sol; in the process, the dipping time is controlled to be 1 s, the pulling speed is controlled to be 0.5 cm/s, a uniformly coated pre-carrier is obtained, then the carrier is placed in a constant temperature humidity drying box to be dried for more than 72 h, and is roasted for 2 h in a high-temperature furnace with air as a sintering atmosphere at the temperature of 750 ℃, and the gamma-Al with the thickness of 1.0 mu m is prepared on a zirconia hollow fiber substrate2O3Transition layer, final preparation of ZrO2@γ-Al2O3A substrate.
(3) Preparation of pure Defect-free-UiO-66 film
At ZrO2@γ-Al2O3Preparing an ultrathin pure Defect-free-UiO-66 film on a substrate: ZrO with both ends sealed by unsintered tape2@γ-Al2O3The substrate is vertically arranged in a polytetrafluoroethylene reaction kettle according to ZrCl4：H2BDC: DMF ═ 1: 1: preparing synthetic mother liquor of the UiO-66 film according to the molar ratio of 500, uniformly stirring, and then crystallizing in situ for 16 hours at the temperature of 220 ℃ to prepare the complete and continuous metal organic framework Defect-free-UiO-66 (film) with a complete crystal structure.
Example 3
1.γ-Al2O3The method for preparing the ceramic-based pure ML-UiO-66 forward osmosis membrane by modifying the ceramic substrate by the intermediate layer comprises the following steps:
(1) preparation of pure ML-UiO-66 film
ZrO prepared in the third section2@γ-Al2O3Preparing an ultrathin ML-UiO-66 film on a substrate: ZrO with both ends sealed by unsintered tape2@γ-Al2O3The substrate is vertically arranged in a polytetrafluoroethylene reaction kettle according to ZrCl4：H2BDC：CH3COOH: DMF ═ 1: 1: 25: preparing a synthetic mother solution of the ML-UiO-66 film according to a molar ratio of 500, uniformly stirring, and then carrying out in-situ crystallization for 48 hours at a temperature of 120 ℃ to prepare a complete and continuous metal organic framework ML-UiO-66 (ML: Msing-linker) film with crystal internal defects.
The application of the pure UiO-66 membrane, the complete pure UiO-66 membrane is put into a hollow fiber membrane module to be used for water treatment. Because the aperture of the pure UiO-66 membrane is larger than the dynamic diameter of water, and the hydrophilic pure UiO-66 membrane has good hydrophilicity, a low-resistance water transmission channel can be provided for water molecules, and simultaneously, hydrated ions of salt can be effectively intercepted, so that the membrane performance is improved, and the membrane can be used for a forward osmosis process. In addition, the stable coordination capacity of the Zr clusters in the pure UiO-66 membrane ensures the stable operation of the pure UiO-66 membrane in acidic, alkaline and high-chlorine water environments, so that the pure UiO-66 membrane can be directly used for real wastewater treatment.
2. Application effect of ceramic-based pure UiO-66 forward osmosis membrane in forward osmosis of water solvent
In this work, it was demonstrated that pure UiO-66 membranes have good application prospects in the forward osmosis field. Applied to a Defect-free-UiO-66 film: in the running process of taking 1M NaCl solution as an extraction solution and deionized water as a raw material solution, the water flux reaches 9.9 +/-1.2L M–2 h–1While maintaining a low reverse salt flux of only 1.84 + -0.4 g m–2h–1. The water flux increased with increasing draw solution concentration, the detailed results are shown in figure 8, while the reverse salt flux remained essentially constant.
Application to ML-UiO-66 membranes: in the running process of taking 1M NaCl solution as an extraction solution and deionized water as a raw material solution, the water flux reaches 14.3 +/-0.6L M–2 h–1While maintaining a low reverse salt flux of only 2.84 + -0.3 g m–2 h–1. The water flux increased with increasing draw solution concentration, the detailed results are shown in figure 9, while the reverse salt flux remained essentially constant.
3. Research on acid and alkali resistance of ceramic-based ML-UiO-66 forward osmosis membrane
The acid and alkali resistance of ML-UiO-66 membranes was measured in water environments with pH =3, 5, 7, 9, 11, operating a forward osmosis unit. As shown in FIG. 10, the ceramic-based ML-UiO-66 film shows better stability in a series of aqueous solutions with different pH values.
4. Research on real petrochemical wastewater of a ceramic-based ML-UiO-66 forward osmosis membrane.
In order to investigate the actual wastewater treatment effect of the ML-UiO-66 membrane, the effluent of the secondary sedimentation tank of the Shanghai petrochemical plant was used to investigate the treatment effect. The experimental result is shown in fig. 11, the ceramic-based ML-UiO-66 membrane shows good stability in the treatment process of petrochemical wastewater, and still keeps good stable operation in the long-term operation process of 1 d.
Claims (8)
1. The method for modifying the ceramic-based TFN forward osmosis membrane by using the titanium dioxide intermediate layer is characterized by comprising the following steps:
s1, preparation of mullite ceramic carrier
Dissolving polyether sulfone and additive polyvinylpyrrolidone in N-methyl pyrrolidone, wherein the mass ratio of polyether sulfone: polyvinylpyrrolidone: n-methyl pyrrolidone =1:0.1-0.2:4-6, and ball milling is carried out to completely dissolve the N-methyl pyrrolidone so as to prepare polymer slurry;
then adding the fly ash and bauxite with the material ratio of 0.85:1 into the polymer slurry to obtain casting mold slurry with the solid content of 40-55 wt%, and continuously ball-milling for more than 48 h to ensure uniform dispersion; vacuumizing the casting film slurry for 2 h to remove residual bubbles, pouring the casting film slurry into a slurry tank, applying nitrogen pressure to the slurry tank by using deionized water as an inner core liquid, immersing a fiber wet film extruded from a spinning nozzle into deionized water of an external solidification bath through an air gap of 15-30 cm, and gelling and curing for 24 h to form a hollow fiber film green body; sintering at 1200 ℃ and 1400 ℃ to obtain the mullite ceramic carrier;
s2. preparation of titanium dioxide interlayer
Putting the mullite ceramic carrier with the aperture of 400-700 nm into an ethanol solution for washing for 30-60min, then washing the mullite ceramic carrier clean by deionized water, and putting the mullite ceramic carrier into an oven for drying;
preparing an inorganic transition layer on a ceramic hollow fiber substrate: firstly, preparing titanium dioxide suspension with the concentration of 10-20 wt%, and uniformly coating the outer surface of the ceramic hollow fiber substrate by using a dip-coating process; in the process, the dipping time is controlled to be 5-10 s, the pulling speed is controlled to be 0.5-1.5 cm/s, and the carrier is placed in a constant-temperature humidity drying box for drying for more than 12 h after being dipped; roasting for 10-12 hours at the temperature of 500-900 ℃ in a high-temperature furnace with air as a sintering atmosphere, and preparing a titanium dioxide transition layer with the thickness of 3.0-5.0 mu m on a ceramic hollow fiber substrate;
s3 Synthesis of MOF-801 powder
Mixing fumaric acid and ZrOCl2·8H2Dissolving O in a mixed solvent of N-N dimethylformamide and formic acid, stirring for 10-30 min by using an electromagnetic stirrer until the O is dissolved, and reacting for 24 h at 100-150 ℃; after the reaction is finished, centrifuging the solution after the reaction for 5-10 min under the condition that the rotating speed is 6000-10000 rpm to obtain white precipitate; washing the white precipitate with N-N dimethylformamide for 48-72 h, and then exchanging with anhydrous methanol for 48-72 h; finally, placing the white precipitate in a vacuum drying oven to be activated for 24-48 h under the condition of 100-180 ℃ to obtain MOF-801; the fumaric acid: ZrOCl2·8H2The molar ratio of O is 1:1-5, the volume ratio of N-N dimethylformamide to formic acid in the mixed solvent is 10-2: 1
S4, synthesis of ceramic-based TFN forward osmosis membrane
Putting 0.02-0.1 wt% MOF-801 into 0.1-0.4 wt% trimesoyl chloride solution, performing ultrasonic treatment for 30-60min, and preparing 2-5 wt% m-phenylenediamine solution; the ceramic substrate modified by the titanium dioxide middle layer is placed in m-phenylenediamine solution for 3-10 min, then dried for 5-10 min at room temperature, reacted in trimesoyl chloride solution for 1-3 min, and finally the sample is placed in a 60-90 ℃ oven for 5-10 min for further reaction to prepare the ceramic-based TFN forward osmosis membrane.
2. The application of the TFN forward osmosis membrane prepared by the method for modifying the ceramic-based TFN forward osmosis membrane by the titanium dioxide interlayer according to claim 1 is characterized in that: the TFN forward osmosis membrane is applied to a seawater desalination process.
3. The application of the TFN forward osmosis membrane prepared by the method for modifying the ceramic-based TFN forward osmosis membrane by the titanium dioxide interlayer according to claim 1 is characterized in that: the TFN forward osmosis membrane is applied to forward osmosis of an organic solvent.
4. The application of the TFN forward osmosis membrane prepared by the method for modifying the ceramic-based TFN forward osmosis membrane by the titanium dioxide interlayer according to claim 3 is characterized in that: the kinetic diameter of the organic solvent molecules is less than or equal to the diameter of the polyamide membrane or the diameter of the MOF-801 powder.
5. The application of the TFN forward osmosis membrane prepared by the method for modifying the ceramic-based TFN forward osmosis membrane by the titanium dioxide interlayer according to claim 3 is characterized in that: the organic solvent is ethanol or methanol.
A method of a UiO-66 doped ceramic based TFN forward osmosis membrane, characterized by the steps of:
s1, preparation of mullite ceramic carrier
Dissolving polyether sulfone and additive polyvinylpyrrolidone in N-methyl pyrrolidone, wherein the mass ratio of polyether sulfone: polyvinylpyrrolidone: n-methyl pyrrolidone =1:0.1-0.2:4-6, and ball milling is carried out to completely dissolve the N-methyl pyrrolidone so as to prepare polymer slurry;
then adding the fly ash and bauxite with the material ratio of 0.85:1 into the polymer slurry to obtain casting mold slurry with the solid content of 40-55 wt%, and continuously ball-milling for more than 48 h to ensure uniform dispersion; vacuumizing the cast membrane slurry for 2 hours to remove residual bubbles, pouring the cast membrane slurry into a slurry tank, applying nitrogen pressure to the slurry tank, immersing a wet fiber membrane extruded from a spinneret into deionized water of an external solidification bath through an air gap of 15-30 cm, and gelling and curing for 24 hours to obtain a hollow fiber membrane green body; sintering at 1200 ℃ and 1400 ℃ to obtain the mullite ceramic carrier;
s2. preparation of titanium dioxide interlayer
Putting the mullite ceramic carrier with the aperture of 400-700 nm into an ethanol solution for washing for 30-60min, then washing the mullite ceramic carrier clean by deionized water, and putting the mullite ceramic carrier into an oven for drying;
preparing an inorganic transition layer on a ceramic hollow fiber substrate: firstly, preparing titanium dioxide suspension with the concentration of 10-20 wt%, and uniformly coating the outer surface of the ceramic hollow fiber substrate by using a dip-coating process; in the process, the dipping time is controlled to be 5-10 s, the pulling speed is controlled to be 0.5-1.5 cm/s, and the carrier is placed in a constant-temperature humidity drying box for drying for more than 12 h after being dipped; roasting for 10-12 hours at the temperature of 500-900 ℃ in a high-temperature furnace with air as a sintering atmosphere, and preparing a titanium dioxide transition layer with the thickness of 3.0-5.0 mu m on a ceramic hollow fiber substrate;
s3 Synthesis of UiO-66 powder
Mixing terephthalic acid and ZrCl4Dissolving the mixture in a mixed solvent of N-N dimethylformamide and acetic acid, stirring the mixture until the mixture is dissolved, and reacting at 120-220 ℃; after the reaction is finished, centrifuging the reaction solution to obtain a white precipitate; washing with N-N dimethylformamide for 48-72 h, and then exchanging with anhydrous methanol for 48-72 h; vacuum drying and activating to obtain UiO-66; the terephthalic acid: ZrCl4The molar ratio of N-N dimethylformamide to acetic acid in the mixed solvent is 1:1-5, and the volume ratio of N-N dimethylformamide to acetic acid in the mixed solvent is 10-2: 1;
s4, synthesis of ceramic-based TFN forward osmosis membrane
Putting 0.02-0.1 wt% of UiO-66 into 0.1-0.4 wt% of trimesoyl chloride solution, performing ultrasonic treatment for 30-60min, and preparing 2-5 wt% of m-phenylenediamine solution; the ceramic substrate modified by the titanium dioxide middle layer is placed into a m-phenylenediamine solution for 3-10 min, dried for 5-10 min at room temperature, reacted in a trimesoyl chloride solution for 1-3 min, and finally the sample is placed into a 60-90 ℃ oven for 5-10 min for further reaction to prepare the UiO-66 doped ceramic-based TFN forward osmosis membrane.
7. The preparation method of the pure UiO-66 forward osmosis membrane is characterized by comprising the following steps:
(1) preparation of zirconia ceramic carrier
Preparing a zirconia green body by using zirconia powder as a raw material through a wet spinning-phase conversion method, and calcining at high temperature to obtain a zirconia ceramic carrier;
（2）γ-Al2O3preparation of the intermediate layer
Preparing oxide gamma-Al2O3Sol, coating uniform gamma-Al on the outer surface of the zirconia hollow fiber substrate by using a dipping process2O3Sol; preparation of ZrO2@γ-Al2O3A substrate;
(3) preparation of pure UiO-66 forward osmosis membrane
The pure UO-66 forward osmosis membrane comprises a pure Defect-free-UO-66 membrane and a pure ML-UO-66 membrane, wherein the preparation of the pure Defect-free-UO-66 membrane comprises the following steps:
at ZrO2@γ-Al2O3Preparing a pure Defect-free-UiO-66 film on a substrate: ZrO 2 is mixed with2@γ-Al2O3The substrate is vertically arranged in a polytetrafluoroethylene reaction kettle according to ZrCl4: terephthalic acid: DMF ═ 1-5: 1-5: preparing a synthetic mother solution according to the molar ratio of 500 plus 600, uniformly stirring, and then carrying out in-situ crystallization to prepare a metal organic framework UiO-66 film with a complete crystal structure, namely a Defect-free-UiO-66 film;
preparation of pure ML-UiO-66 film
At ZrO2@γ-Al2O3Preparation of pure ML-UiO-66 film on substrate: ZrO 2 is mixed with2@γ-Al2O3The substrate is vertically arranged in a polytetrafluoroethylene reaction kettle according to ZrCl4: terephthalic acid: CH (CH)3COOH: DMF ═ 1-5: 1-5: 20-50: preparing synthetic mother liquor of the UO-66 film according to the molar ratio of 500-600, uniformly stirring, and carrying out in-situ crystallization to prepare the complete and continuous metal organic framework ML-UO-66 film with the internal defects of the crystal.
8. Use of a pure UiO-66 forward osmosis membrane prepared according to the method of claim 7, wherein: the pure UiO-66 forward osmosis membrane is applied to petrochemical wastewater treatment.
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| CN117018888B (en) * | 2023-05-08 | 2024-05-10 | 南京工业大学 | MOF-801@CS pervaporation membrane and application thereof in methanol/dimethyl carbonate separation |
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