CN114471200B - Method for improving preparation of Zr-based MOF membrane by using intermediate modification layer and forward osmosis application of Zr-based MOF membrane - Google Patents

Method for improving preparation of Zr-based MOF membrane by using intermediate modification layer and forward osmosis application of Zr-based MOF membrane Download PDF

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CN114471200B
CN114471200B CN202210149307.2A CN202210149307A CN114471200B CN 114471200 B CN114471200 B CN 114471200B CN 202210149307 A CN202210149307 A CN 202210149307A CN 114471200 B CN114471200 B CN 114471200B
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CN114471200A (en
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王栋
杨文涛
董应超
赵志育
孙阔
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Dalian University of Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D71/02—Inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/002—Forward osmosis or direct osmosis
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    • B01D—SEPARATION
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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Abstract

A method for improving preparation of Zr-based MOF membrane by an intermediate modification layer and forward osmosis application thereof belong to the technical field of environmental membrane separation. The nano composite titanium dioxide intermediate layer is introduced, so that the surface property of the supporting layer is improved, good growth conditions are provided for interfacial polymerization, meanwhile, novel porous nano materials MOF-801 and UiO-66 are introduced, a more compact polyamide layer is grown, the porous MOF-801 and UiO-66 materials provide additional low-resistance transmission channels for the transmission of water and solvent molecules, the water flux and the organic solvent flux are improved, meanwhile, the proper pore diameters of the polyamide membrane, MOF-801 and UiO-66 can effectively block the passage of salt ions, so that the reverse salt flux is reduced, and the problem of membrane permeability and selectivity trade-off can be effectively solved. To further increase the permeability and stability of the membranes, pure UiO-66 membranes (Defect-free-UiO-66 and ML-UiO-66) were developed for use in forward osmosis processes with significant success. Provides a new thought and a new method for the structural design of the active layer of the forward osmosis membrane.

Description

Method for improving preparation of Zr-based MOF membrane by using intermediate modification layer and forward osmosis application of Zr-based MOF membrane
Technical Field
The invention relates to a ceramic-based TFThe preparation technology of N forward osmosis membrane provides a titanium dioxide intermediate layer modified ceramic substrate, and introduces a method for preparing a defect-free ceramic-based TFN forward osmosis membrane by novel materials MOF-801 and UiO-66, and simultaneously has gamma-Al 2 O 3 The application of the pure UiO-66 membrane of the modification layer in developing a new forward osmosis field belongs to the technical field of environmental membrane separation.
Background
The membrane separation technology is very widely focused due to the advantages of low energy consumption, high efficiency, environmental friendliness and the like, and has important application prospects in the aspects of solving the environmental and energy problems. The forward osmosis technology is widely focused on the advantages of low cost, low pollution, high water recovery rate and the like.
As the core forward osmosis membrane of forward osmosis technology (FO), which is the core of forward osmosis technology, TFC membranes (thin film composite membranes) are currently mainly the main, membrane permeability and selectivity trade-off and long-term stability problems of the support are also some challenges facing forward osmosis technology at present. The forward osmosis membrane reported in the current literature is mainly made of organic carriers, and compared with the organic carriers, the inorganic carriers have the advantages of high mechanical strength, high thermal stability, high chemical stability and the like, but the traditional ceramic carriers have higher cost. The mullite ceramic support prepared by using the industrial solid waste fly ash and the low-cost bauxite as raw materials not only reduces the cost of the ceramic support, but also increases the recycling value of the industrial solid waste and reduces the environmental hazard of the industrial solid waste.
The preparation of polyamide membranes directly on organic supports is very easy, because the surface pore size of the organic support is small and the roughness is low; the mullite ceramic carrier has larger surface pore diameter and larger roughness, so that the polyamide layer grows in the pores, the grown polyamide layer is defective, the effective film thickness is increased, and further, the resistance encountered during water transmission is increased, so that the water flux is smaller, and the reverse salt flux is larger. This is detrimental to forward osmosis applications.
The pure UiO-66 membrane has wide application because of the advantages of high stability, adjustable aperture and the like, and mainly relates to: a pervaporation process and a reverse osmosis process. At present, no research on the forward osmosis process of a pure UiO-66 membrane exists, and the main challenges are that the reverse salt flux is too high due to poor compactness of the prepared membrane, and the water flux is low due to the fact that the pore size cannot be adjusted.
Disclosure of Invention
The invention aims to provide a titanium dioxide intermediate layer 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 simultaneously, a pure UiO-66 membrane is applied to a forward osmosis process, so that the prepared membrane has a great prospect in the fields of sea water desalination and 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 into a ceramic substrate modified by a titanium dioxide intermediate layer comprises the following steps:
(1) Preparation of mullite ceramic carrier
The mullite ceramic carrier is prepared from industrial solid waste fly ash and bauxite serving as raw materials by a wet spinning-phase inversion method, and by high-temperature calcination.
(2) Preparation of Titania interlayers
(2.1) putting the mullite ceramic carrier with the pore diameter of 600-800 and nm into ethanol solution for washing for 30-60min, then washing with deionized water, and putting into an oven for drying.
(2.2) preparation of an inorganic transition layer on a ceramic hollow fiber substrate: firstly, preparing titanium dioxide suspension with the concentration of 10-20wt% and uniformly coating the outer surface of a ceramic hollow fiber substrate by using an immersion pulling process; in the process, the dipping time is controlled to be 5-10 s, the lifting speed is controlled to be 0.5-1.5 cm/s, a successfully dipped carrier is obtained, the carrier is placed in a constant temperature and humidity drying box to be dried over 12 and h, the carrier is baked at the temperature of 500-900 ℃ in a high-temperature furnace with the sintering atmosphere of air for 10-12 h, and a titanium dioxide transition layer with the thickness of 3.0-5.0 mu m is prepared on a ceramic hollow fiber substrate.
(3) Synthesis of MOF-801 powder
Fumaric acid (0.081 g,3.5 mmol) and ZrOCl 2 ·8H 2 O (0.23 g,0.70 mmol) is dissolved in a mixture solvent of DMF/formic acid (35 mL/5.3 mL), stirred by an electromagnetic stirrer for 10-30 min until the solute is dissolved, and then placed in a reaction kettle to react in a 100-150 ℃ oven for 24-h. And after the reaction is finished, centrifuging the reacted solution 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 hours, carrying out 2-4 times per day, and exchanging with absolute methanol for 48-72 hours, wherein the times per day are 2-4 times per day. And finally, placing the white precipitate in a vacuum drying oven to be activated for 24-48 hours at the temperature of 100-180 ℃ to obtain the usable MOF-801, and sealing and preserving the MOF-801 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 MOF-801 with the concentration of 0.02-0.1wt% into TMC solution with the concentration of 0.1-0.4wt% for ultrasonic treatment for 30-60min, and then preparing MPD solution with the concentration of 2-5wt%. Firstly, putting a ceramic substrate modified by a titanium dioxide intermediate layer into an MPD solution for 3-10 min, then drying for 5-10 min at room temperature, reacting for 1-3 min in a TMC solution, and finally, putting a sample into 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 evaluate the integrity of ceramic-based TFN forward osmosis membrane composite membranes, the salt rejection rate (Rs) of the membrane was measured using a cross-flow reverse osmosis device. The selectivity of the membranes was tested at a transmembrane pressure of 3-6 bar. And before starting measurement, pre-pressing for 30-60min to ensure the stability of the measured value. The water permeability is obtained by measuring the water flux through the membrane. The rejection was measured using a sodium chloride solution having a concentration of 200 ppm. R is R s For retention rate, C f And C p The concentration (mol/L) of the permeate and the concentration (mol/L) of the raw material liquid are respectively.
Figure 7122DEST_PATH_IMAGE002
(6) Application of ceramic-based TFN forward osmosis membrane
Application of ceramic-based TFN forward osmosis membranes, a defect-free ceramic-based TFN forward osmosis membrane is placed in a hollow fiber membrane module for water treatment. Because the pore diameters of the polyamide membrane and MOF-801 and UiO-66 powder in the ceramic-based TFN forward osmosis membrane are larger than the kinetic diameter of water, and meanwhile, the hydrophilic Zr-MOF has excellent water absorption capacity and proper pore diameter, an additional low-resistance water transmission channel can be provided for water molecules, and meanwhile, salt ions can be effectively trapped, so that the membrane performance is improved, and the ceramic-based TFN forward osmosis membrane can be used for sea water desalination. Also, in terms of organic solvent recovery, the pore diameters of the polyamide membrane and the MOF-801 and UiO-66 powder are larger than the hydrated ion radius of ethanol and smaller than the hydrated ion radius of monovalent salt ions, and the mullite carrier, the polyamide membrane and the MOF-801 powder are very stable in the ethanol solvent, so that the porous membrane and the porous membrane can be used for forward osmosis application of the organic solvent.
The method for preparing the UiO-66 doped ceramic-based TFN forward osmosis membrane comprises the following steps:
s1, preparation of mullite ceramic carrier
Dissolving polyethersulfone and an additive polyvinylpyrrolidone into N-methyl pyrrolidone, wherein the polyethersulfone is as follows: polyvinylpyrrolidone: n-methylpyrrolidone=1:0.1-0.2:4-6, ball milling to dissolve completely, preparing polymer slurry;
then adding the fly ash and bauxite with the material ratio of 0.85:1 into the polymer slurry to obtain casting mould slurry with the solid content of 40-55 wt%, and continuously ball-milling for more than 48 h to ensure uniform dispersion; the casting film slurry is firstly vacuumized for 2 h to remove residual bubbles, then poured into a slurry tank, the inner core liquid is deionized water, nitrogen pressure is applied, the fiber wet film extruded from a spinning nozzle is immersed into the deionized water in an external coagulating bath through an air gap of 15-30 cm, and the fiber wet film is gelled and solidified into a hollow fiber film green body through 24 h; sintering at 1200-1400 ℃ to obtain a mullite ceramic carrier;
s2, preparation of a titanium dioxide intermediate layer
Putting the mullite ceramic carrier with the aperture of 400-700 and nm into ethanol solution for washing for 30-60min, then washing with deionized water, and putting 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 10-20wt% and uniformly coating the outer surface of a ceramic hollow fiber substrate by using an immersion pulling process; in the process, the dipping time is controlled to be 5-10 s, the lifting speed is controlled to be 0.5-1.5 cm/s, and the carrier is placed in a constant temperature and humidity drying box to be dried for more than 12 h after dipping; roasting 10-12 h in a high-temperature furnace with the sintering atmosphere of air at the temperature of 500-900 ℃ to prepare 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
Terephthalic acid and ZrCl 4 Dissolving in a mixed solvent of N-N dimethylformamide and acetic acid, stirring for 10-30 min by an electromagnetic stirrer until the mixture is dissolved, and reacting at 120-220 ℃ for 24-h; after the reaction is finished, centrifuging the reacted solution for 5-10 min under the condition that the rotating speed is 6000-10000 rpm, so as to obtain white precipitate; washing the white precipitate with N-N dimethylformamide for 48-72 h, and exchanging with absolute methanol for 48-72 h; finally, placing the white precipitate in a vacuum drying oven to be activated for 24-48 hours at the temperature of 100-180 ℃ to obtain UIO-66; the terephthalic acid: zrCl 4 The mol ratio of the N-N dimethylformamide to the acetic acid in the mixed solvent is 1:1-5, and the volume ratio of the N-N dimethylformamide to the acetic acid is 10-2:1, a step of;
s4, synthesis of ceramic-based TFN forward osmosis membrane
Placing UiO-66 with the concentration of 0.02-0.1wt% into trimesic chloride solution with the concentration of 0.1-0.4wt% for ultrasonic treatment for 30-60min, and then preparing m-phenylenediamine solution with the concentration of 2-5wt%; firstly, putting a ceramic substrate modified by a titanium dioxide intermediate layer into m-phenylenediamine solution for 3-10 min, then drying for 5-10 min at room temperature, reacting for 1-3 min in trimesoyl chloride solution, and finally, putting a sample into 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-Al 2 O 3 Middle layer modified ceramic substrate, and is madeThe method for preparing the ceramic-based pure Defect-free-UiO-66 forward osmosis membrane comprises the following steps:
(1) Preparation of zirconia ceramic carrier
Zirconia powder with the grain size of 200nm in industry is used as a raw material, zirconia green bodies are prepared by a wet spinning-phase inversion method, and then the zirconia ceramic carrier is obtained by high-temperature calcination.
（2）γ-Al 2 O 3 Preparation of the intermediate layer
Preparing oxide gamma-Al with concentration of 0.05-0.2wt% 2 O 3 Sol, coating uniform gamma-Al on the outer surface of zirconia hollow fiber substrate by using dipping process 2 O 3 Sol; 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 and humidity drying box to be dried over 72 h, and baked to-2 h in a high temperature furnace with the sintering atmosphere being air at 750 ℃ to prepare the gamma-Al with the thickness of-1.0 mu m on the zirconia hollow fiber substrate 2 O 3 A transition layer, finally preparing ZrO 2 @γ-Al 2 O 3 A substrate.
(3) Preparation of pure Defect-free-UiO-66 film
In ZrO 2 @γ-Al 2 O 3 Preparation of ultra-thin ML-UiO-66 film on substrate: zrO sealing both ends with raw material tape 2 @γ-Al 2 O 3 The substrate is vertically arranged in a polytetrafluoroethylene reaction kettle and is prepared according to ZrCl 4 ：H 2 BDC: dmf=1-5: 1-5: preparing a synthetic mother solution of the UiO-66 film in a molar ratio of 500-600, uniformly stirring, and crystallizing in situ at 220 ℃ for 16 hours to prepare the complete and continuous metal organic frame Defect-free-UiO-66 film with crystal internal defects.
(IV) gamma-Al 2 O 3 The method for preparing the ceramic-based pure ML-UiO-66 forward osmosis membrane by modifying the ceramic substrate through the intermediate layer comprises the following steps:
(1) Preparation of pure ML-UiO-66 film
ZrO produced in section (III) 2 @γ-Al 2 O 3 Preparation of ultra-thin ML-UiO-66 film on substrate: zrO sealing both ends with raw material tape 2 @γ-Al 2 O 3 The substrate is vertically arranged in a polytetrafluoroethylene reaction kettle and is prepared according to ZrCl 4 ：H 2 BDC：CH 3 COOH: dmf=1-5: 1-5:20-50: preparing a synthetic mother solution of the ML-UIO-66 film in a molar ratio of 500-600, uniformly stirring, and crystallizing 48-h in situ at a temperature of 120 ℃ to prepare a complete and continuous metal organic framework ML-UIO-66 (ML: mssing-linker) film with internal defects of crystals.
(2) Application of pure UiO-66 forward osmosis membrane
The Defect-free-UiO-66 membrane and the ML-UiO-66 (ML: msting-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 pore diameter of the pure UiO-66 membrane is larger than the kinetic 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 meanwhile, hydrated ions of salt can be effectively trapped, so that the pure UiO-66 membrane can be used for a forward osmosis process. In addition, the stable coordination capacity of 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 prepare a defect-free polyamide membrane on an inorganic ceramic carrier, we introduce TiO 2 An intermediate layer, which covers the macropores on the surface of the mullite carrier to form uniform micropores and a smoother surface, thus leading to the polyamide layer only on the TiO 2 The surface of the intermediate layer grows to form a polyamide layer with a smaller thickness, and the degree of crosslinking is also improved, which means that the film is more compact. But the water flux is affected, and optimization is required to improve the membrane performance.
In order to further improve the membrane performance, MOFs have good compatibility with polyamide membranes, and MOFs have inorganic and organic characteristics, which facilitate the formation of relatively ideal interfacial voids with polyamide without sacrificing membrane selectivity. In addition, metal Organic Frameworks (MOFs) are used as novel porous materials, and have the advantages of high porosity, proper pores, specific surface area and the like. Because the hydrophilic MOF-801 has excellent 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 trade-off problem of membrane permeability and selectivity can be effectively overcome, and meanwhile, the mullite ceramic carrier has the advantages of high mechanical strength, high thermal stability, high chemical stability and the like, and the long-term stability problem is effectively solved. The prepared defect-free ceramic-based forward osmosis membrane has a good application prospect in the sea water desalination field and the forward osmosis application of organic solvents:
(1) An inorganic ceramic support was used as a 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 novel carrier for preparing the high-performance forward osmosis membrane.
(2) The nano composite titanium dioxide intermediate layer is introduced, the surface property of the support layer is changed, good growth conditions are provided for interfacial polymerization, meanwhile, a novel porous nano material MOF-801 is introduced, a more compact PA layer is grown, the porous MOF-801 material provides an additional low-resistance transmission channel for water transmission, and meanwhile, the proper aperture also effectively blocks the passage of salt ions, so that the reverse salt flux is reduced, and a new thought and a new method are provided for improving the structure and performance of the active layer.
(3) Compared with a 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 film crystal and the research of forward osmosis process widen the application range for the application of forward osmosis technology, and can be particularly well 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 mullite ceramic supports.
FIG. 3 is a diagram of a mullite-titania composite membrane electron microscope.
Fig. 4 is a pore size and roughness characterization of mullite-titania composite membranes.
FIG. 5 is a ceramic-based TFN forward osmosis membrane electron microscope image.
FIG. 6 is a graph of the performance of a ceramic-based TFN forward osmosis membrane for desalinating seawater.
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 forward osmosis performance of ceramic-based ML-UiO-66 membranes.
FIG. 10 is a graph of acid and alkali resistance stability of ceramic-based ML-UIO-66 membranes.
FIG. 11 is a graph of the real petrochemical wastewater treatment performance of ceramic-based ML-UiO-66 membranes.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings and technical schemes.
Example 1
1. Preparation of mullite carrier:
the mullite green compact is prepared by taking fly ash and bauxite as raw materials through a wet spinning-phase inversion method. First, PES of 16 g and 2 g PVP as an additive were dissolved in NMP of 64 g, and ball-milled 6h to completely dissolve them, thereby preparing a polymer slurry. Then adding 46 g fly ash and 54 g bauxite into the polymer solution, and continuously ball-milling for more than 48 h to ensure uniform ball milling. The prepared casting film slurry was first vacuumized 2 h until the residual air bubbles were removed. Then pouring the fiber wet film into a slurry tank, wherein the inner core liquid is deionized water, the flow rate is 30 mL/min, the nitrogen pressure is applied at 0.1 MPa, the fiber wet film extruded from the spinneret is immersed into the deionized water in an external coagulation bath through an air gap of 15 cm, and the fiber wet film is gelled and solidified into a hollow fiber film green body through 24 h. And sintering at 1250 ℃ to characterize the morphology, the pore diameter and the roughness of the mullite sample, wherein the pore diameter of the surface of the carrier is larger, the average pore diameter is about 550 nm, the roughness is Ra=169 nm, as shown in fig. 1 and 2, and the defective polyamide membrane is easy to generate.
2. Preparation of mullite-titanium dioxide composite film
20wt% of anatase nano TiO 2 Powder, 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 ball milling is performed on 48 and h to uniformly mix the materials. 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 obtained 2 A suspension.
Uniformly coating the outer surface of the ceramic hollow fiber substrate by using an immersion lifting process; in the process, the dipping time is controlled to be 5 s, the lifting speed is controlled to be 1 cm/s, a successfully dipped carrier is obtained, the carrier is placed in a constant temperature and humidity drying box to be dried over 12 h, and is baked at the temperature of 800 ℃ in a high-temperature furnace with the sintering atmosphere of air for 12 h, so that the titanium dioxide transition layer with the thickness of 5.0 mu m is prepared on the ceramic hollow fiber substrate. Characterization is carried out on the morphology, the pore diameter and the roughness of the obtained mullite-titanium dioxide composite membrane sample, as shown in fig. 3 and 4, the surface pore diameter is larger, the average pore diameter is about 300 nm, and the roughness is ra=31 nm, which indicates that the existence of titanium dioxide reduces the pore diameter and the roughness, and is favorable for forming a compact polyamide membrane.
Preparation of MOF-801 powder
0.401 g fumaric acid and 0.23g zirconium oxychloride are dissolved in 35ml N-N dimethylformamide and 3.5 ml formic acid solution, stirred by an electromagnetic stirrer until solute is dissolved, and then placed in a reaction kettle to react in a 120 ℃ oven for 24 h. After the reaction, the reacted solution was centrifuged at 8000 rpm for 5 min to obtain a white precipitate. The white precipitate was washed 72 h with N-N dimethylformamide 3 times daily and exchanged 72 h with anhydrous methanol 3 times daily. Finally, placing the white precipitate in a vacuum drying oven to activate 24 h at 150 ℃ to obtain the usable MOF-801, and sealing and preserving the MOF-801 to prevent the MOF-801 from absorbing moisture in the air.
4. Preparation of ceramic-based TFN forward osmosis membrane
The preparation of the ceramic-based TFN film is to introduce an emerging MOF-801 material, and the MOF-801 material is unstable under alkaline conditions (the pH of m-phenylenediamine dissolved in water is 9-10), so that the MOF-801 with the concentration gradient of 0.04-0.12 wt% is put into an n-hexane solution for ultrasonic treatment, so that the MOF-801 is uniformly dispersed. Then, as in the process of preparing the TFC membrane, the mullite-titanium dioxide composite membrane is immersed in m-phenylenediamine solution for 3min, then dried in air until no macroscopic water drops exist, and then immersed in TMC solution containing MOF-801 for interfacial polymerization for 1 min. The film after preparation was subjected to a subsequent heat treatment (5 min) at 60 ℃ in an oven. The prepared film is preserved in deionized water, and an electron microscope image of the film is shown as figure 5, and the surface of the TFN film has the shape of ridge valley polyamide and the MOF-801 of regular octahedron, so that the successful preparation of the ceramic-based TFN film is proved.
Evaluation of 5 ceramic-based TFN Forward osmosis Membrane integrity
The salt rejection rate (Rs) of the membrane was measured using a cross-flow reverse osmosis device. The membrane was tested for permeability and selectivity at a transmembrane pressure of 5 bar. Pre-pressing for 60min before starting measurement ensures the stability of the measured value. From the test results, the rejection rate of the ceramic-based TFN forward osmosis membrane reaches 95%, which shows that the forward osmosis membrane is complete, compact and defect-free.
6. Ceramic-based TFN forward osmosis membrane seawater desalination application effect
The porous ceramic mullite is taken as a substrate for the first time, and a titanium dioxide transition layer modification strategy is provided for preparing the defect-free ceramic-based TFN forward osmosis membrane. The synthesized ceramic-based TFN forward osmosis membrane is used for sea water desalination, and the specific experiment is as follows: deionized water is used as raw material liquid, 1M NaCl is used as drawing liquid, and performance test is carried out on the prepared film.
As can be seen from FIG. 6, the water flux in FO mode of direct preparation of Forward osmosis membrane on mullite support is 6.9.+ -. 1.2. 1.2L/m 2 h, reverse salt flux of 10+ -0.7 g/m 2 h, indicating that the forward osmosis membrane directly prepared on the mullite carrier is defective, so that salt ions pass through.
Preparation of Forward osmosis Membrane on Titania modified support the water flux of the Forward osmosis Membrane in FO mode was 13.74+ -0.9L/m 2 h, reverse salt flux of 5.2+ -0.5 g/m 2 h, compared with the forward osmosis membrane directly prepared on the mullite carrier, the water flux is improved, the reverse salt flux is reduced, and the dioxygen is proved to be compared with the forward osmosis membrane directly prepared on the carrierThe forward osmosis membrane prepared on the titanium-modified carrier is more compact and thinner.
On a carrier modified by titanium dioxide, introducing a novel material MOF-801 to prepare a TFN forward osmosis membrane, wherein the water flux of the TFN forward osmosis membrane in a FO mode is 22+/-0.9L/m 2 h, reverse salt flux of 3.9+ -0.5 g/m 2 h. Compared with the former two, the ceramic-based TFN forward osmosis membrane has improved water flux and reverse salt flux, which indicates that the ceramic-based TFN forward osmosis membrane is complete and has no defect, and MOF-801 does provide an additional low-resistance water transmission channel for water molecules, and meanwhile, salt ions are effectively trapped, so that the ceramic-based TFN forward osmosis membrane has good effect in sea water desalination application.
In order to further study the anti-pollution performance of the ceramic-based TFN forward osmosis membrane in actual seawater, a pollution prevention test is carried out by adopting 250 mg/L sodium alginate as a model pollutant. As can be seen from fig. 7, the ceramic-based TFN forward osmosis membrane flux after stable operation is higher than the ceramic-based TFC forward osmosis membrane flux, which shows to some extent that the ceramic-based TFN forward osmosis membrane has better anti-pollution performance, and the more hydrophilic membrane surface is easier to form a water layer to prevent the hydrophobic adhesion of sodium alginate. After washing, the water flux of the ceramic-based TFC forward osmosis membrane can be restored to about 75% of the original flux, and the ceramic-based TFN forward osmosis membrane can be restored to about 90%, which shows that the pollution of the ceramic-based TFN forward osmosis membrane can achieve a better result through physical washing to a certain extent, namely the pollution is reversible.
7. Forward osmosis application effect of ceramic-based TFN forward osmosis membrane organic solvent
Because the pore diameter of the polyamide membrane (about 0.5 and nm) or the pore diameter of the MOF-801 powder (average of 0.6 and nm) is larger than the kinetic diameter of ethanol molecules (0.44 and nm) and smaller than the hydrated ion diameters of monovalent lithium ions (0.76 and nm) and chloride ions (0.66 and nm), the mullite carrier, the polyamide membrane and the MOF-801 powder are very stable in ethanol solvent, and the prepared ceramic-based TFN forward osmosis membrane can be used for forward osmosis application of organic solvent. In the experimental process, ethanol is adopted as raw material liquid, 2M lithium chloride is dissolved in ethanol as drawing liquid, and experimental results show that the ceramic-based TFN forward osmosis membrane is communicated with ethanol under the AL-FS modeThe amount reaches 3.5+/-0.3L/m 2 h, reverse salt flux of 0.8+ -0.2 g/m 2 h, the retention rate of enrofloxacin can reach 99.7%, which shows that the ceramic-based TFN forward osmosis membrane has good effect in organic solvent forward osmosis application.
For other organic solvents, the porcelain-based TFN forward osmosis membrane also has a higher solvent flux. Taking methanol as an organic solvent as an example, the kinetic diameter (0.38 and nm) of molecules of the methanol 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 under the AL-FS mode 2 h, reverse salt flux of 1.6+ -0.17 g/m 2 h。
Example 2
1.γ-Al 2 O 3 The method for preparing the ceramic-based pure Defect-free-UiO-66 forward osmosis membrane by modifying the ceramic substrate with the intermediate layer comprises the following steps:
(1) Preparation of zirconia ceramic carrier
Zirconia powder with the grain size of 200nm in industry is used as a raw material, zirconia green bodies are prepared by a wet spinning-phase inversion method, and then the zirconia ceramic carrier is obtained by high-temperature calcination.
（2）γ-Al 2 O 3 Preparation of the intermediate layer
Preparing oxide gamma-Al with concentration of 0.1wt% 2 O 3 Sol, coating uniform gamma-Al on the outer surface of zirconia hollow fiber substrate by using dipping process 2 O 3 Sol; in the above 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 and humidity drying box to be dried over 72 h, and is baked in a high temperature furnace with the sintering atmosphere of air at 750 ℃ for 2 h, and the gamma-Al with the thickness of 1.0 μm is prepared on the zirconia hollow fiber substrate 2 O 3 A transition layer, finally preparing ZrO 2 @γ-Al 2 O 3 A substrate.
(3) Preparation of pure Defect-free-UiO-66 film
In ZrO 2 @γ-Al 2 O 3 Ultrathin pure Defect-free-UiO-66 film was prepared on the substrate: will beZrO with tape seals at both ends 2 @γ-Al 2 O 3 The substrate is vertically arranged in a polytetrafluoroethylene reaction kettle and is prepared according to ZrCl 4 ：H 2 BDC: dmf=1: 1: preparing a synthetic mother solution of the UiO-66 membrane in a molar ratio of 500, uniformly stirring, and crystallizing 16h in situ at 220 ℃ to prepare the complete and continuous metal organic frame Defect-free-UiO-66 (membrane) with a complete crystal structure.
Example 3
1.γ-Al 2 O 3 The method for preparing the ceramic-based pure ML-UiO-66 forward osmosis membrane by modifying the ceramic substrate through the intermediate layer comprises the following steps:
(1) Preparation of pure ML-UiO-66 film
ZrO produced in section (III) 2 @γ-Al 2 O 3 Preparation of ultra-thin ML-UiO-66 film on substrate: zrO sealing both ends with raw material tape 2 @γ-Al 2 O 3 The substrate is vertically arranged in a polytetrafluoroethylene reaction kettle and is prepared according to ZrCl 4 ：H 2 BDC：CH 3 COOH: dmf=1: 1:25: preparing a synthetic mother solution of the ML-UiO-66 film in a molar ratio of 500, uniformly stirring, and crystallizing 48 and h in situ at a temperature of 120 ℃ to prepare the complete and continuous metal organic framework ML-UiO-66 (ML: mssing-linker) film with crystal internal defects.
Application of pure UiO-66 membrane the complete pure UiO-66 membrane is put into a hollow fiber membrane module for water treatment. The pore diameter of the pure UiO-66 membrane is larger than the kinetic 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 meanwhile, hydrated ions of salt can be effectively trapped, 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 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. Ceramic-based pure UiO-66 forward osmosis membrane water solvent forward osmosis application effect
In this work, it was demonstrated that pure UiO-66 membranes have good application in the forward osmosis fieldAnd (3) prospect. The method is applied to the Defect-free-UiO-66 film: in the running process of taking 1M NaCl solution as the drawing liquid and taking deionized water as the raw material liquid, the water flux reaches 9.9+/-1.2L M –2 h –1 While maintaining a low reverse salt flux of only 1.84.+ -. 0.4 g m –2 h –1 . The water flux increases with increasing draw solution concentration, detailed results are shown in fig. 8, while the reverse salt flux remains substantially stable.
Application to ML-UIO-66 film: in the running process of taking 1M NaCl solution as the drawing liquid and taking deionized water as the raw material liquid, the water flux reaches 14.3+/-0.6L M –2 h –1 While maintaining a low reverse salt flux of only 2.84.+ -. 0.3 g m –2 h –1 . The water flux increases with increasing draw solution concentration, detailed results are shown in fig. 9, while the reverse salt flux remains substantially stable.
3. Acid and alkali resistance study of ceramic-based ML-UiO-66 forward osmosis membrane
Acid and alkali resistance of ML-UiO-66 membranes were measured in aqueous environments at ph=3, 5, 7, 9, 11, operating forward osmosis units. The experimental results are shown in FIG. 10, and the ceramic-based ML-UiO-66 film has better stability in a series of aqueous solutions with different pH values.
4. Ceramic-based ML-UiO-66 forward osmosis membrane real petrochemical wastewater research.
To study the actual wastewater treatment effect of the ML-UiO-66 membrane, the secondary sedimentation tank effluent from Shanghai petrochemical plant was used to study the treatment effect. The experimental result is shown in FIG. 11, the ceramic-based ML-UiO-66 membrane has good stability in the petrochemical wastewater treatment process, and still keeps good stable operation in the long-term operation process of 1 d.

Claims (5)

1. The method for modifying the ceramic-based TFN forward osmosis membrane by the titanium dioxide intermediate layer is characterized by comprising the following steps:
s1, preparation of mullite ceramic carrier
Dissolving polyethersulfone and an additive polyvinylpyrrolidone into N-methyl pyrrolidone, wherein the polyethersulfone is as follows: polyvinylpyrrolidone: n-methylpyrrolidone=1:0.1-0.2:4-6, ball milling to dissolve completely, preparing polymer slurry;
then adding the fly ash and bauxite with the material ratio of 0.85:1 into the polymer slurry to obtain casting mould slurry with the solid content of 40-55 wt%, and continuously ball-milling for more than 48 h to ensure uniform dispersion; the casting film slurry is firstly vacuumized for 2 h to remove residual bubbles of reaction, then poured into a slurry tank, the inner core liquid is deionized water, nitrogen pressure is applied, the fiber wet film extruded from a spinning nozzle is immersed into the deionized water of an external coagulation bath through an air gap of 15-30 cm, and the fiber wet film is gelled and solidified into a hollow fiber film green body through 24 h; sintering at 1200-1400 ℃ to obtain a mullite ceramic carrier;
s2, preparation of a titanium dioxide intermediate layer
Putting the mullite ceramic carrier with the aperture of 400-700 and nm into ethanol solution for washing for 30-60min, then washing with deionized water, and putting 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 10-20wt% and uniformly coating the outer surface of a ceramic hollow fiber substrate by using an immersion pulling process; in the process, the dipping time is controlled to be 5-10 s, the lifting speed is controlled to be 0.5-1.5 cm/s, and the carrier is placed in a constant temperature and humidity drying box to be dried for more than 12 h after dipping; roasting 10-12 h in a high-temperature furnace with the sintering atmosphere of air at the temperature of 500-900 ℃ to prepare 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
Fumaric acid and ZrOCl 2 ·8H 2 O is dissolved in a mixed solvent of N-N dimethylformamide and formic acid, stirred by an electromagnetic stirrer for 10-30 min until the O is dissolved, and reacted at 120-150 ℃ for 24 h; after the reaction is finished, centrifuging the reacted solution for 5-10 min under the condition that the rotating speed is 6000-10000 rpm, so as to obtain white precipitate; washing the white precipitate with N-N dimethylformamide for 48-72 h, and exchanging with absolute methanol for 48-72 h; finally, placing the white precipitate in a vacuum drying oven to be activated for 24-48 hours at 150-180 ℃ to obtain MOF-801; the fumaric acid: zrOCl 2 ·8H 2 Molar ratio of O1:1-5, 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 MOF-801 with the concentration of 0.02-0.1wt% into trimesic chloride solution with the concentration of 0.1-0.4wt% for ultrasonic treatment for 30-60min, and then preparing m-phenylenediamine solution with the concentration of 2-5wt%; firstly, putting a ceramic substrate modified by a titanium dioxide intermediate layer into m-phenylenediamine solution for 3-10 min, then drying for 5-10 min at room temperature, reacting for 1-3 min in trimesoyl chloride solution, and finally, putting a sample into a 60-90 ℃ oven for 5-10 min for further reaction to prepare the ceramic-based TFN forward osmosis membrane.
2. The use of the TFN forward osmosis membrane prepared by the method for modifying a ceramic-based TFN forward osmosis membrane with a titanium dioxide interlayer according to claim 1, wherein the TFN forward osmosis membrane is characterized in that: the TFN forward osmosis membrane is applied to the sea water desalination process.
3. The use of the TFN forward osmosis membrane prepared by the method for modifying a ceramic-based TFN forward osmosis membrane with a titanium dioxide interlayer according to claim 1, wherein the TFN forward osmosis membrane is characterized in that: the TFN forward osmosis membrane is applied to organic solvent forward osmosis.
4. The use of a TFN forward osmosis membrane prepared by the method for modifying a ceramic-based TFN forward osmosis membrane with a titanium dioxide interlayer according to claim 3, wherein: the dynamic diameter of the organic solvent molecules is smaller than or equal to the diameter of the polyamide membrane or the diameter of the MOF-801 powder.
5. The use of a TFN forward osmosis membrane prepared by the method for modifying a ceramic-based TFN forward osmosis membrane with a titanium dioxide interlayer according to claim 3, wherein: the organic solvent is ethanol or methanol.
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